KR100490766B1 - Composite materials for cookware - Google Patents

Abstract

Cookware composites do not require complex processes and are made by applying a material made of a fluorine-containing polymer having excellent adhesion to a substrate to the substrate, and are heat-resistant, non-adhesive, antifouling, and water- and oil-repellent property. ), Dirt removal, chemical resistance, rust prevention, antibacterial, resistance to energy ray, and wear resistance is excellent. The composite material is (a) 0.05 to 30 mol% of at least one fluorine-containing ethylenic monomer having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carbonate group, a carboxyester group and an epoxy group, and (b) the It is made by applying to a substrate a material made of a functional group-containing fluorinated ethylenic polymer obtained by copolymerizing 70 to 99.95 mol% of at least one fluorine-containing ethylenic monomer having no functional group.

Description

Composites for Cooking Appliances {COMPOSITE MATERIALS FOR COOKWARE}

Prior art

The present invention applies to a substrate a fluorinated polymer having excellent heat resistance, non-adhesiveness, transparency (designability), antifouling property, and water-and oil repelling property, and particularly excellent adhesion to a substrate. It relates to a composite material for a cooking appliance.

In the cooking apparatus represented by a hot plate and a rice cooker, it is desired to be able to cook at a higher temperature in order to shorten the cooking time and to pursue the taste of the food obtained by cooking. In addition, such a device is desired to be easily arranged after cooking, and it is desired to easily remove dirts such as oil and burning. Moreover, it is also desired that the design is good because it relates to the appearance of the article.

In response to such a request, fluorine-containing resins having excellent heat resistance, chemical resistance, weather resistance, surface characteristics (low friction resistance, etc.), electrical insulation, and the like have been applied to composite materials used in cooking appliances in the form of paints or films.

However, the said fluorine-containing resin has the intrinsic problem that adhesiveness with base materials, such as a metal or glass, is not enough because of its outstanding non-adhesive property.

Therefore, in the case of applying the fluorine-containing resin in the form of a coating, there is a method of chemically or physically roughening the surface of the metal and expecting the anchor effect between the fluorine-containing resin and the base material and bringing it into close contact. . However, this method takes time for the roughening treatment itself, and the adhesive strength is also obtained at an early stage, but it causes attenuation of the anchor effect when the repetitive temperature is applied or used at high temperatures.

A method of chemically activating the surface of the fluorine-containing resin surface by treating with a solution of metal sodium dissolved in liquid ammonia is also proposed. However, this method has a problem that the treatment liquid itself may cause environmental pollution, and at the same time there is a risk in handling thereof.

In addition, a method of activating the surface by physicochemical treatment such as plasma sputtering on the surface of the fluorine-containing resin has also been proposed, but this method has a problem such as that it takes time or costs increase.

Moreover, the addition of various components for improving adhesiveness to a fluorine-containing resin material, or forming a plasma layer is also examined.

For example, there is a technique of adding an inorganic acid such as chromic acid to a coating composition containing a fluorine-containing resin to form a chemical film on the metal surface, thereby enhancing the adhesion (Japanese Patent Publication No. 63-2675). However, since chromic acid contains hexavalent chromium, it cannot be said that both food stability and work stability are sufficient. In addition, when other inorganic acids such as phosphoric acid are used, there is a problem of impairing the stability of the fluorine-containing resin.

Instead of the inorganic acid, heat-resistant resins such as polyamideimide, polyimide, polyether sulfone, polyether ether ketone and the like, and metal powders are further added to the coating material containing a fluorine-containing resin to prepare a primer. Forming a layer is examined (Japanese Patent Laid-Open No. H6-6-4000). However, the fluorine-containing resin and the heat-resistant resin are almost incompatible with each other, and phase separation and the like occur during coating of the membrane, and are likely to cause phase separation between the primer layer and the upper coating layer of the fluorine-containing resin. In addition, due to the difference in the heat shrinkage ratio between the fluorine-containing resin and the heat resistant resin, the decrease in the elongation of the coating film due to the addition of the heat resistant resin, and the like, pinholes at the time of high temperature processing and use, paint film defects such as cracks, and the like are likely to occur. In addition, these heat-resistant resins are difficult to use in applications where whiteness, vivid coloring, transparency, and the like are inferior in designability because browning occurs during firing. In addition, when the heat resistant resins are mixed, the non-tackiness and low friction resistance of the fluorine-containing resin inherently decreases.

In addition, in the adhesion of fluorinated resin coating materials to glass substrates requiring transparency, the surface of the substrate is treated with a silane coupling agent, or silicone resins are added to the fluorine-containing resin paint to improve the adhesiveness (Japan Patent Publication No. 54-42366, Japanese Patent Application Laid-open No. Hei 5-177768, etc., and the improvement of adhesive property are inadequate, heat resistance falls, and peeling, foaming, and coloring are easy to occur at the time of baking or high temperature use.

As fluorine-containing resins, copolymerization of hydrocarbon-based (non-fluorine) monomers containing functional groups such as hydroxyl groups and carboxyl groups has been studied. It is difficult to use in the use which requires the heat resistance of 200-350 degreeC to be used, and the use which requires non-adhesive property, low friction property, etc.

In other words, copolymerization of a hydrocarbon-based (non-fluorine-based) monomer containing a functional group is likely to cause thermal decomposition from the monomer constituents during processing or use at high temperatures, resulting in coating film breakage, coloring, foaming, peeling, and the like. The purpose of the fluorinated resin superintendent cannot be achieved.

In addition, fluorine-containing resins generally have insufficient mechanical strength and dimensional stability, and are expensive in terms of price. Therefore, in order to minimize these drawbacks and to make the most of the said advantage which a fluorine-containing polymer originally has, the application to a film form is also examined.

However, the fluorine-containing resin is inherently low in adhesive strength, and it is difficult to directly bond the fluorine-containing polymer to another material (substrate) in the form of a film. For example, even when adhesion is attempted by thermal fusion or the like, even if the adhesive strength is insufficient or even if there is a certain adhesive strength, the adhesive strength tends to be uneven depending on the type of the substrate, and the adhesive reliability is insufficient. Many.

As a method of bonding the fluorine-containing resin film and the substrate,

1. Method of physically roughening the surface of the substrate by sand blast treatment, etc.

2. A method of subjecting the fluorine-containing resin film to surface treatment such as chemical treatment such as sodium etching, plasma treatment or photochemical treatment;

3. How to glue using glue

Although the above etc. are mainly examined, the said 1 and 2 require a process process, a process is complicated, and productivity is bad. Moreover, the kind and shape of a base material are limited. Originally, the adhesive strength is also insufficient, and appearance problems (designability) such as coloring or color of the obtained composite material are also likely to occur. Moreover, the method of using chemicals, such as sodium etching, also has a problem with stability.

Examination of said adhesive agent 3 is also performed variously. In general, hydrocarbon-based (non-fluorine) adhesives have insufficient adhesiveness and have insufficient heat resistance of their own, and are generally unacceptable in adhesive processing conditions for fluorinated polymer films that require molding or processing at high temperatures. It does not, and causes peeling, coloring, etc. by decomposition. The laminate using the adhesive also has insufficient heat resistance, chemical resistance, and water resistance, so that adhesive strength cannot be maintained due to temperature change or environmental change, and thus lacks reliability.

Moreover, the examination of the adhesive agent using the fluorine-containing polymer which has a functional group, and adhesive composition is performed.

For example, a fluorine-containing polymer obtained by graft polymerization of a hydrocarbon monomer having a carboxyl group, a carbonic anhydride residue, an epoxy group, and a hydrolyzable silyl group represented by maleic anhydride or vinyltrimethoxysilane, etc. Reports used for adhesives (for example, Japanese Patent Application Laid-Open No. 7-18035, Japanese Patent Application Laid-Open No. 7-25952, Japanese Patent Application Laid-Open No. 7-25954, Japanese Patent Application Laid-Open No. 7-173230, Japanese Patent Application Laid-Open No. 7-173446, Each publication of Japanese Patent Application Laid-Open No. 7-173447) or a fluorine-containing copolymer obtained by copolymerizing a hydrocarbon monomer containing a functional group such as hydroxylalkyl vinyl ether with tetrafluoroethylene or chlorotrifluoroethylene, and an isocyanate curing agent. The adhesive composition with and hardened | cured, and the report (for example, Unexamined-Japanese-Patent No. 7-228848) used for the adhesive agent of ETFE with salt ratio and corona discharge treatment is made | formed.

 The adhesive or adhesive composition using a fluorine-containing resin obtained by graft polymerization or copolymerization of these hydrocarbon-based functional monomers is insufficient in heat resistance, and decomposes and foams when processing a composite with a fluorine-containing resin film at high temperature or at high temperature. Or the like to reduce the adhesive strength, peel off, or color. In the adhesive composition described in JP-A-7-228848, the fluorine-containing resin film requires a corona discharge treatment.

As such, no composite material for a cooking appliance is firmly adhered to the base material that satisfies the above request and has excellent design.

In view of the above matters, an object of the present invention is to provide a composite material for a cooking appliance, which is made by applying a material made of a fluorine-containing polymer excellent in adhesion to a substrate to a substrate without requiring a complicated process.

In addition, the present invention is to provide a composite for cooking equipment excellent in non-adhesiveness, antifouling property, water and oil repellency, dirt removal, chemical resistance, rust prevention, antibacterial, resistance to energy ray, low friction.

Disclosure of the Invention

The present invention is (a) 0.05 to 30 moles of at least one monomer of the functional group-containing fluorinated ethylenic monomer having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carbonate group, a carboxyester group and an epoxy group. % Wow,

(b) for a cooking appliance comprising applying to a substrate a material comprising a functional group-containing fluorine-containing ethylenic polymer having a functional group formed by copolymerizing at least 70 to 99.95 mol% of at least one monomer of the fluorine-containing ethylenic monomer having no functional group Relates to a composite material.

In this case, the functional group-containing fluorine-containing ethylenic monomer (a) is represented by the formula (1):

CX ₂ = CX ¹ -R _f -Y (1)

(Wherein Y is —CH ₂ OH, —COOH, carbonate, carboxyester group or epoxy group, X and X ¹ are the same or differently hydrogen or fluorine atom, R _f is divalent fluorinated alkyl having 1 to 40 carbon atoms) At least 1 represented by a rene group, a fluorine-containing oxyalkylene group having 1 to 40 carbon atoms, a fluorine-containing alkylene group containing an ether group having 1 to 40 carbon atoms, or a fluorine-containing oxyalkylene group containing an ether bond having 1 to 40 carbon atoms). It is preferable that it is a functional group containing fluorine-containing ethylenic monomer of a species.

Moreover, it is preferable that the fluorine-containing ethylenic monomer (b) which does not have the said functional group is tetrafluoroethylene.

Further, the fluorine-containing ethylenic monomer (b) having no functional group is 85 to 99.7 mol% of tetrafluoroethylene and formula (2):

CF ₂ = CF-R _f ¹ (2)

(Wherein, R _f ¹ is preferably a mixed monomer with 0.3 to 15 mol% of monomers represented by CF ₃ or OR _f ² (R _f ² is a C 1-5 perfluoroalkyl group).

In addition, it is preferable that the fluorine-containing ethylenic monomer (b) which does not have the said functional group is a mixed monomer of 40-80 mol% of tetrafluoroethylene, 20-60 mol% of ethylene, and 0-15 mol% of other copolymerizable monomers. Do.

The present invention also relates to a composite for cooking appliance, wherein the functional group-containing fluorinated ethylenic polymer is applied to a substrate in the form of a paint.

The present invention also relates to a composite for cooking appliance, wherein the functional group-containing fluorine-containing ethylenic polymer is applied to a substrate in the form of an aqueous acid solution.

The present invention further relates to a composite for cooking appliance, wherein the functional group-containing fluorine-containing ethylenic polymer is applied to the substrate in the form of powder coating.

The present invention also relates to a composite for cooking appliance, wherein the functional group-containing fluorinated ethylenic polymer is applied to a substrate in the form of a film.

It is preferable that the said base material is a metallic base material.

Moreover, it is preferable that the said base material is a glass base material.

The present invention relates to a cooking appliance formed by using the above-described cooking appliance composite material.

Moreover, this invention relates to the heating cooking appliance which uses the said composite material for cooking appliances.

Moreover, this invention relates to the hotplate which uses said composite material for cooking appliances.

Moreover, this invention relates to the hotplate which uses the said composite material for cooking appliances for a metal heating surface.

Moreover, this invention relates to the hotplate which uses said cooker composite material for glass lids.

Moreover, this invention relates to the oven range which uses said composite material for cooking appliances.

Moreover, this invention relates to the oven range which uses the said composite material for cooking appliances for a metal inner surface.

Moreover, this invention relates to the oven range which uses the said cooking appliance composite material for a cooking plate.

Moreover, this invention relates to the oven range which uses said composite material for cooking appliances for a door made of glass.

Moreover, this invention relates to the heating pan which uses the said composite material for cooking appliances.

Moreover, this invention relates to the heating pan which uses the said composite material for cooking appliances for a metal heating surface.

Moreover, this invention relates to the heating pan which uses said composite material for cooking appliances for a glass lid.

Moreover, this invention relates to the frying pan which uses said composite material for cooking appliances.

Moreover, this invention relates to the frying pan which uses said cooker composite material for a metal heating surface.

Moreover, this invention relates to the fryer which uses the said composite material for cooking appliances.

Moreover, this invention relates to the fryer which uses the said composite material for cooking appliances for a metal inner surface.

Moreover, this invention relates to the fryer which uses the said composite material for cooking appliances for the inner surface of glass.

Moreover, this invention relates to the rice cooker which uses the said composite material for cooking appliances.

Moreover, this invention relates to the rice cooker which uses the said composite material for cooking appliances for a metal inner surface.

Moreover, this invention relates to the rice cooker which uses said composite material for cooking appliances for a metal inner lid.

Moreover, this invention relates to the jar which uses the said composite material for cooking appliances.

Moreover, this invention relates to the jar which uses the said composite material for cooking appliances for a metal inner surface.

Moreover, this invention relates to the jar which uses said composite material for cooking appliances for a metal inner lid.

Moreover, this invention relates to the tableware or container which uses said composite material for cooking appliances.

Moreover, this invention relates to the metal tableware or container which uses said composite material for cooking appliances.

Moreover, this invention relates to the glass tableware or container which uses said composite material for cooking appliances.

The present invention also relates to a food processing cooker using the above-mentioned cooking appliance composite material.

In addition, the present invention relates to a cooking appliance for food mixing, which uses the above-mentioned cooking appliance composite.

In addition, the present invention relates to a food cutting processing cooking appliance made using the above-mentioned cooking appliance composite material.

Moreover, this invention relates to the bakery apparatus which uses the said composite material for cooking appliances.

Brief description of the drawings

1 is a schematic plan view of an adhesive sample prepared for measuring the adhesive strength in Example 7 of the present invention.

Fig. 2 is a schematic perspective view of the measuring instrument used for measuring the adhesive strength in Example 7 of the present invention.

It is a schematic perspective view of the laminated body produced in order to obtain the test piece used for the adhesion test (T-type peeling test) in this invention.

It is a schematic perspective view of the test piece used for the adhesion test (T-type peeling test) in this invention.

5 is a schematic perspective view of a test piece used for the adhesion test (tensile shear test) in the present invention.

6 is a schematic explanatory diagram of a test apparatus used for the adhesion test (tensile shear test) in the present invention.

7 is a schematic cross-sectional view of the laminate test plate produced in Example 15 of the present invention.

8 is a schematic sectional view of a three-layer laminate obtained in Example 15 of the present invention.

9 is a schematic sectional view of a laminate obtained in Comparative Example 10 of the present invention.

10 is a schematic cross-sectional view of a laminate test plate produced to obtain a laminate in Example 16 of the present invention.

11 is a schematic sectional view of a laminate obtained in Example 16 of the present invention.

It is a schematic sectional drawing of the laminated body used for the T-type peeling test performed in Example 16 of this invention.

It is a schematic sectional drawing of the laminated body used for the T type peeling test performed by the comparative example 10 of this invention.

14 is a schematic cross-sectional view of the laminate test piece produced in Comparative Example 12 of the present invention.

It is a schematic perspective view of the test piece used for the non-adhesive test in the Example of this invention.

16 is a schematic perspective view of an aluminum plate having a coating film obtained in Example 19 (1) of the present invention.

Fig. 17 is a schematic perspective view of the measuring instrument for measuring the adhesive strength obtained in Example 19 (2).

18 is a schematic cross-sectional view of the laminate test plate produced in Example 22. FIG.

19 is a schematic cross-sectional view of a three-layer laminate obtained in Example 22 of the present invention.

Embodiment of the invention

The composite material for a cooking appliance of the present invention comprises (a) at least one of a functional group-containing fluorinated ethylenic monomer having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carbonate, a carboxyl ester group and an epoxy group. 0.05-30 mol% of monomers of a species,

(b) The material which consists of a fluorine-containing ethylenic polymer which has a functional group formed by copolymerizing 70-99.95 mol% of at least 1 sort (s) of monomers of the fluorine-containing ethylenic monomer which does not have said functional group is applied to a base material.

The material comprising the functional group-containing fluorine-containing polymer has a use of an adhesive, a surface treatment of the substrate, formation of a primer layer, and adhesion to the material in the form of a paint or a film with respect to metal, glass, and other substrates. It has surprisingly strong adhesion even without adding the component.

The functional group-containing fluorine-containing polymer used to obtain the composite material of the present invention is copolymerized with the fluorine-containing ethylenic monomer (b) having no functional group by using the functional group-containing fluorine-containing ethylenic monomer of the above (a), It is important to introduce functional groups into the fluorine-containing polymer, and therefore, it is possible to impart excellent adhesion directly to various substrate surfaces which are conventionally inadequate or impossible. In other words, even if the functional group-containing fluorine-containing polymer is excellent in heat resistance as compared with the copolymerization of the non-fluorine-based functional group-containing monomer, thermal decomposition at the time of processing at a high temperature (for example, 200 to 400 ° C, etc.) is less suppressed, A large adhesive strength can be obtained, and a coating layer free from coloring or foaming, pinholes, leveling defects, and the like can be formed on the substrate. Moreover, also when using a composite material at high temperature, adhesiveness is maintained and defects of coating layers, such as coloring, whitening, foaming, and pinhole, are hard to generate | occur | produce further.

In addition, the functional group-containing fluorine-containing polymer has not only heat resistance but also excellent properties such as chemical resistance, non-adhesiveness, antifouling property, low friction resistance, weather resistance, etc., of the fluorine-containing polymer, so as not to deteriorate these excellent properties. Can be given without.

Next, a functional group-containing fluorine-containing ethylenic copolymer, which is a material of the composite material of the present invention, will be described first.

The functional group of the functional group-containing fluorine-containing ethylenic polymer is at least one selected from a hydroxyl group, a carboxyl group, a carbonate, a carboxyl ester group and an epoxy group, and can provide adhesion to various substrates by the effect of the functional group. It is. Although the kind and combination of functional groups are suitably selected according to the kind, purpose, or use of the surface of a base material, it is most preferable to have a hydroxyl group from a heat resistant viewpoint.

As said functional group containing fluorine-containing ethylenic monomer (a) which is one of the components which comprise this functional group containing fluorine-containing ethylenic polymer, it is (a-1) Formula (1):

CX ₂ = CX ¹ -R _f -Y (1)

(Wherein Y is —CH ₂ OH, —COOH, carbonate, carboxyester group or epoxy group, X and X ¹ are the same or differently hydrogen or fluorine atom, R _f is divalent fluorinated alkyl having 1 to 40 carbon atoms) Functional group containing an ene group, a fluorine-containing oxyalkylene group having 1 to 40 carbon atoms, a fluorine-containing alkylene group containing an ether group having 1 to 40 carbon atoms, or a fluorine-containing oxyalkylene group containing an ether bond having 1 to 40 carbon atoms). It is preferable that it is a fluorine-containing ethylenic monomer.

Moreover, as a specific example of a functional group containing fluorine-containing ethylenic monomer (a-1), Formula (3):

CF ₂ = CF-R _f ³ -Y (3)

[Wherein, Y is the same as Y in formula (1), and R _f ³ is a divalent fluorinated alkylene group having 1 to 40 carbon atoms or OR _f ⁴ (R _f ⁴ is a divalent fluorinated alkylene group having 1 to 40 carbon atoms). Or a divalent fluorine-containing alkylene group containing an ether bond having 1 to 40 carbon atoms), formula (4):

CF ₂ = CFCF ₂ -OR _f ⁵ -Y (4)

[Wherein Y is the same as Y in formula (1), R _f ⁵ represents a divalent fluorine-containing alkylene group having 1 to 39 carbon atoms or a divalent fluorine-containing alkylene group containing ether bonds having 1 to 39 carbon atoms) ], Equation (5):

CH ₂ = CFCF ₂ -R _f ⁶ -Y (5)

[Wherein, Y is the same as Y in formula (1), and R _f ⁶ is a divalent fluorinated alkylene group having 1 to 39 carbon atoms or OR _f ⁷ (R _f ⁷ is a divalent fluorinated alkylene group having 1 to 39 carbon atoms). Or a divalent fluorine-containing alkylene group containing an ether bond having 1 to 39 carbon atoms) or formula (6):

CH ₂ = CH-R _f ⁸ -Y (6)

[Wherein, Y is equal to Y, and the R _f of formula (1) ⁸ is a divalent fluorine-containing alkylene group of 1 to 40 carbon atoms], and the like will appear in.

Since the copolymerizability with the fluorine-containing ethylenic monomer (b) which does not have a functional group in the functional group containing fluorine-containing ethylenic monomer of Formula (3)-formula (6) is comparatively favorable, and the heat resistance of the polymer obtained by copolymerization is remarkable. It is preferable for the reason which does not fall.

Among them, the compounds of the formulas (3) and (5) are preferred in view of copolymerizability with the fluorine-containing ethylenic monomer (b) having no functional group and from the heat resistance of the obtained polymer, and particularly the compounds of formula (5) desirable.

As a functional group containing fluorine-containing ethylenic monomer represented by Formula (3), More specifically,

Etc. are illustrated.

As a functional group containing fluorine monomer represented by Formula (4),

Etc. are illustrated.

As a functional group containing fluorine monomer represented by Formula (5),

Etc. are illustrated.

As a functional group containing fluorine monomer represented by Formula (6),

Etc. are illustrated.

etc,

And the like.

The fluorine-containing ethylenic monomer (b) containing no functional group copolymerized with the functional group-containing fluorine-containing ethylenic monomer (a) can be appropriately selected from known monomers, and polymers of heat resistance, chemical resistance, non-tackiness, antifouling property, and low friction can be To give.

Specific examples of fluorine-containing ethylenic monomer (b), tetrafluoroethylene, formula _{(2): CF 2 = CF} -R f 1 [R f 1 is CF ₃ or OR _f ² (R _f ² is of 1 to 5 carbon atoms Perfluoroalkyl group), chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, hexafluoroisobutene,

(Wherein X ² is selected from a hydrogen atom, a chlorine atom or a fluorine atom, n is an integer of 1 to 5), and the like.

Further, in addition to the functional group-containing fluorine-containing ethylenic monomer (a) and the fluorine-containing ethylenic monomer (b) not having the functional group, an ethylenic monomer having no fluorine atom in a range that does not reduce heat resistance or non-tackiness. You may copolymerize. In this case, the ethylenic monomer having no fluorine atom is preferably selected from an ethylenic monomer having 5 or less carbon atoms in order not to lower the heat resistance, and specific examples thereof include ethylene, propylene, 1-butene, 2-butene, and the like. have.

The content rate of the functional group containing fluorine-containing ethylenic monomer (a) in the functional group containing fluorine-containing ethylenic polymer used by this invention is 0.05-30 mol% of the total amount of the monomer in a polymer. Moreover, although it selects suitably according to the difference of the kind, shape, coating method, film formation method, conditions, purpose, use, etc. of the surface of the base material for cooking appliances, Preferably it is 0.05-20 mol%, Especially preferably, it is 0.1-10 mol % to be.

If the content of the functional group is less than 0.05%, it is difficult to sufficiently obtain adhesion to the surface of the base material, and peeling or the like is likely to occur due to temperature change, infiltration of chemicals, or the like. In addition, when it exceeds 30 mol%, the heat resistance is lowered, resulting in poor adhesion, coloring, foaming, pinholes, etc. during firing at a high temperature or use at a high temperature, resulting in deterioration of design properties, peeling of the coating layer, or thermal decomposition products. It is easy to cause elution.

Preferred examples of the functional group-containing fluorine-containing ethylenic polymer used in the present invention are as follows.

(I) Polymer (I) (reactive PTFE) of 0.05-30 mol% of functional group containing fluorine-containing ethylenic monomer (a-1), and 70-99.95 mol% of tetrafluoroethylene.

This polymer is excellent in the point which is excellent in heat resistance, chemical-resistance, and non-tackiness, and has sliding property (low friction resistance, abrasion resistance).

(II) Tetrafluoroethylene containing 0.05-30 mol% of functional group containing fluorine-containing ethylenic monomer (a-1) with respect to the whole quantity of a monomer, and excluding the said monomer (a-1). 85 to 99.7 mol% and the above formula (2):

CF ₂ = CF-R _f ¹ (2)

[R _f ¹ is CF _3, OR _f ² is selected from (R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms); polymers (Ⅱ) monomers with 0.3 to 15 mol% appear to. For example a tetrafluoroethylene-perfluoro (alkylvinylether) copolymer (reactive PFA) having a functional group or a tetrafluoroethylene-hexafluoropropylene polymer having a functional group (reactive FEP).

This polymer has heat resistance, chemical resistance, and non-tackiness which are almost equivalent to the reactive PTFE of (I), and also have transparency and melt molding, and can be transparent and surface smoothed by heat even when applied in the form of a paint. Excellent at

(III) Tetrafluoroethylene containing the functional group-containing fluorine-containing ethylenic monomer (a-1) in an amount of 0.05 to 30 mol% based on the total amount of the monomers, and excluding the monomer (a-1). 40 to 80 mol%, ethylene 20 to 60 mol%, other copolymerizable monomers 0 to 15 mol% (ethylene-tetrafluoroethylene polymer (III) having functional groups (reactive ETFE).

This polymer has excellent heat resistance, antifouling property, and weather resistance, and has excellent transparency, hard mechanical strength with excellent mechanical strength, and excellent melt flow property, so that it is easy to be molded and composited with other substrates. Excellent at one point

The functional group-containing fluorine-containing polymer can be obtained by copolymerizing the functional group-containing fluorinated ethylenic monomer (a) described above with a fluorine-containing ethylenic monomer (b) having no functional group by a known polymerization method. Especially, the method by radical copolymerization is mainly used. That is, in order to start the polymerization, the means is not limited at all as long as it proceeds radically, but is initiated by, for example, organic, inorganic radical polymerization initiator, heat, light or ionizing radiation. Melt polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, etc. can also be used for the kind of polymerization. The molecular weight is controlled by the concentration of the monomer used for the polymerization, the concentration of the polymerization initiator, the concentration of the chain transfer agent, and the temperature. The composition of the resulting copolymer can be controlled by the composition of the monomer to be added.

The functional group-containing fluorine-containing ethylenic polymer described above can take various forms as a material for applying to a substrate. Typically, the form of a coating material or a film-shaped material is mentioned, It is good also as a form of a molded article.

In the present invention, the functional group-containing fluorinated ethylenic polymer may be applied to a substrate in the form of a paint to obtain a composite for a cooking appliance.

In the present invention, when applied to the substrate in the form of a paint, it may take the form of an aqueous acid solution, an organic solvent dispersion, a powder (including the assembly), an organosol, an aqueous emulsion of an organosol. Among them, it is preferable to apply in the form of an aqueous acid solution or a powder (powder coating) in view of the environment and stability.

The paint may be applied in a form in which the functional group-containing fluorine-containing ethylenic polymer exhibits excellent adhesiveness with a substrate, and may be used as a single layer or as a primer layer.

The aqueous component acid solution for fluorine-containing paint in the present invention is obtained by dispersing the particles of the functional group-containing fluorine-containing ethylenic polymer in water. By introducing the functional group into the fluorine-containing polymer, dispersion stability of the fine particles in the aqueous acid solution is improved, and a paint having good storage stability is obtained, and the leveling property and transparency of the film after coating are improved.

As the functional group-containing fluorinated ethylenic polymer, reactive PTFE (I), reactive PFA or reactive FEP (II) is preferable from the viewpoints of heat resistance, non-adhesiveness, and low friction, and reactive PTFE (I), heat resistance, non-adhesiveness and transparency.

It is preferable that the said aqueous component liquid is a composition of the form which the microparticles | fine-particles of the said polymer of 0.01-1.0 micrometer disperse | distributed in water. Generally, the surfactant for dispersion stabilization may be mix | blended in it. In addition, additives such as pigments, surfactants, antifoaming agents, viscosity modifiers, and leveling agents which are commonly used in the aqueous acid solution may be blended in a range that does not significantly lower heat resistance, chemical resistance, non-tackiness, and low friction. Can be.

The aqueous acid solution for fluorine-containing paint can be produced by various methods. Specifically, for example

A method of finely pulverizing a powder of a fluorine-containing polymer having a functional group obtained by a suspension polymerization method, and dispersing it uniformly with a surfactant in an aqueous solvent,

A method of preparing an aqueous fluorine-containing acidic solution at the same time as the polymerization by an emulsion polymerization method and further blending a surfactant or an additive if necessary;

Although the etc. are mentioned, The method of manufacturing an aqueous acidic solution directly by emulsion polymerization method from the surface of productivity and quality (small particle size hardening and uniform particle size hardening) is preferable.

The polymer concentration of the aqueous acid solution varies depending on the target film thickness, the concentration of the coating material, the viscosity, the coating method, and the like, but is usually selected within the range of about 5 to 70% by weight.

A coating method is not specifically limited, What is necessary is just to apply | coat and dry by a brush method, a spray method, the roll coat method, etc., and to bake at the temperature above melting | fusing point of a polymer and below distribution temperature according to the kind of polymer.

Moreover, what is necessary is just to select the film thickness of a coating film suitably according to a use, an objective, a base material, etc., for example, about 5-200 micrometers, Preferably it is 10-100 micrometers.

Powder coating in this invention consists of the powder of the said functional group containing fluorine-containing ethylenic polymer.

Moreover, reactive PFA or reactive FEP (II) is preferred from the viewpoint of heat resistance, non-adhesiveness, corrosion resistance and chemical resistance, and reactive ETFE (III) from the viewpoint of antifouling property, processability and transparency.

The fluorine-containing powder coating is preferably a powder or granule having a particle diameter of 10 µm to 1000 µm and an appearance density of 0.3 to 1.2 g / cc.

In the fluorine-containing powder coating, for example, carbon powder, pigments such as titanium oxide, cobalt oxide, powders such as glass fibers and carbon fibers, mica and the like within a range that does not significantly reduce the performance of fluorine resins such as heat resistance. Additives such as reinforcing agents, amine antioxidants, organosulfur compounds, organotin antioxidants, phenolic antioxidants, heat stabilizers such as metal soaps, leveling agents and antistatic agents can be suitably blended.

Although the said compounding of the said additive to a fluorine-containing powder coating may be mixed (dry) in powder form, and may be mixed (wet) in slurry form, it is preferable to carry out in powder form. As the mixing device, for example, ordinary mixers and grinders such as sand mills, V-type blenders, and ribbon blenders can be used.

The coating of the fluorine-containing powder coating is generally performed by electrostatic spraying, fluidized bed immersion, rotary lining, or the like, and then, depending on the type of polymer, a good coating film is formed by firing at a temperature above the melting point of the polymer and below a decomposition temperature. can do.

In general, in the case of electrostatic powder coating, a coating film having a film thickness of 10 to 200 µm and in the case of rotary lining is formed with a film thickness of 200 to 1000 µm.

Moreover, the functional group containing fluorine-containing ethylenic polymer used for the said fluorine-containing paint material has favorable heat resistance at the time of coating the fluorine resin which does not have a functional group to the surface of base materials, such as a metal and glass, using the adhesiveness. It can also be used as a primer layer for fluorine-containing paints to have.

The primer for fluorine-containing paint consists of the said functional group containing fluorine-containing ethylenic polymer.

The primer can be specifically used the same thing as the above-mentioned fluorine-containing polymer, and it is suitably selected by the kind of surface of a base material, the kind of fluorine-containing polymer coat | covered through a primer, etc. (type of upper coating). Generally, it is preferable that the primer for fluorine-containing coatings contains a functional group in what has a structure equivalent to the structure of the fluorine-containing polymer coat | covered on it.

This combination has good compatibility between the fluorine-containing polymer used for the primer and the fluorine-containing polymer coated thereon, and the adhesion between the surface of the substrate and the interlayer adhesion strength between the primer layer and the upper coating layer may be good. have. Moreover, even when using at high temperature, it is difficult to produce interlaminar peeling, cracks, pinholes or the like due to a difference in thermal contraction rate of the polymer, as in the case of using a primer in which other resin components are added. Moreover, since the whole coating film originally consists of a fluorine-containing polymer, it can fully respond to the use which has transparency and vivid coloring, and also excellent heat resistance for forming a fluorine-containing polymer which does not contain a functional group in the outermost surface of a coating film, The chemical property, non-tackiness, and low friction can be exhibited more effectively.

Examples of the fluorine-containing polymer containing no functional group used for the upper coating layer include PTFE, PFA, FEP, ETFE, PVdF, and VdF-based copolymers.

Specifically, the functional group-containing fluorine-containing ethylenic polymer may be used as the primer for the fluorine-containing paint. However, when the substrate is coated with PTFE, a primer selected from reactive PTFE (I), reactive PFA or FEP (II) It is preferable to use it as a base material, and especially it is preferable to use heat-melting reactive PFA or FEP (II) for a primer because it can hardly heat-melt and adhere | attach on the surface of a base material by baking. When the substrate is coated with PFA or FEP, it is preferable to use reactive PFA or FEP (II) as the primer. In addition, when coating a base material with ETFE, it is especially preferable to use reactive ETFE (III) for a primer from an adhesive point and transparency point.

As a coating method using a primer layer,

(1st process) The process of apply | coating the primer for fluorine-containing paint which consists of a fluorine-containing polymer which has the said functional group to the surface of a base material,

(2nd process) The process of apply | coating the fluorine-containing paint which consists of a fluorine-containing polymer which does not have a functional group on the primer layer formed at the 1st process,

(3rd process) The process of baking the laminated body obtained by the 1st process and the 2nd process

The coating method of the fluorine-containing polymer which consists of three large steps of can be used preferably. Further, the primer layer applied in the first step may be dried to touch over 80 to 150 ° C. for about 5 to 30 minutes, and then proceeded to the next second step (2 coating and 1 firing). In addition, after baking a primer layer at the high temperature more than melting temperature, for example, you may advance to a 2nd process (2 application | coating 2 baking).

The method of applying the primer in the first step is appropriately selected according to the type of the primer, for example, when the fluorine-containing primer is in the form of an aqueous acid solution, a method such as spray coating, spray coating, brush coating, dipping, etc. Is used. In the case of the powder coating, methods such as an electrostatic coating method, a fluid immersion method, a rotary lining method, and the like are used.

Although the thickness of a primer layer may vary with an objective, a use, the kind of surface of a base material, and the form of coating, it is 1-50 micrometers, Preferably it is 2-20 micrometers. Thus, since a primer is generally thin film thickness, it is preferable to apply | coat a primer by spray coating etc. in the form of an aqueous dispersion.

The coating method of the coating material which consists of a fluorine-containing polymer which does not contain the functional group on the primer layer of a 2nd process is suitably selected according to the kind of fluorine-containing polymer, the form of a coating material, a purpose, and a use, For example, In the case of the organic solvent dispersion, spray coating, brush coating, roll coating, spin coating, etc. are generally performed, and in the case of powder coating, coating is performed by electrostatic coating, fluid immersion method, rotary lining method, or the like.

The coating film of the fluorine-containing polymer in this step is completely different depending on the purpose, use, and coating method, and is generally 5 to 50 µm, preferably about 10 to 30 µm, by thick coating using powder coating. When aiming, coating | coating of the film thickness of 20-10 micrometers by the electrostatic coating method and 0.3-10 mm by the rotational lining method is possible.

Although the baking conditions of a 3rd process are suitably selected by the kind (composition, melting | fusing point, etc.) of a fluorine-containing polymer of a primer layer and the upper layer on it, generally, it bakes at the temperature more than melting | fusing point of both fluorine-containing polymers. Although firing time changes with baking temperature, it is 5 minutes-3 hours, Preferably it is about 10 to 30 minutes. For example, when coating PTFE, PFA, FEP, etc., it bakes at 320-400 degreeC, Preferably it is 350-400 degreeC.

Next, a technique for producing a composite for cooking appliance by applying the functional group-containing fluorine-containing ethylenic polymer in the form of a film will be described.

The advantages of applying in the form of a film are as follows.

(1) A film made of a functional group-containing fluorine-containing ethylenic polymer can be adhered to the hot melt adhesive without being required by an applicator, and can be adhered to each other by thermocompression bonding.

(2) In addition, since a uniform adhesive layer is formed on the entire surface of the substrate, uniform adhesive strength without adhesion unevenness can be obtained, and it can cope with a substrate having no compatibility or poor compatibility.

③ It can be cut and used in various shapes, so it is advantageous in terms of low work loss and good working environment.

The fluorine-containing polymer film of the present invention is preferably a fluorine-containing polymer film formed by molding the functional group-containing fluorine-containing ethylenic polymer, and can be adhered to various other substrates without performing surface treatment or general adhesive. Thus, excellent properties of the fluorine-containing polymer can be imparted to the substrate.

Among the functional group-containing fluorine-containing polymers, it is possible to produce an adhesive film using various adhesives depending on the purpose and purpose, the film manufacturing process, and the bonding method, but the adhesive film itself is heat resistant, chemically resistant, mechanical properties, non-tacky, etc. Capable of efficient film molding as represented by melt molding, having good moldability, being capable of thinning and homogenizing, being melted by various thermocompression methods, and being able to firmly and cleanly adhere to various substrates For reasons such as, and the like, the copolymer (III) (reactive PFA or reactive FEP) or the copolymer (IV) (reactive ETFE) is preferred. Moreover, as a functional group, a hydroxyl group is especially preferable at a heat resistant point.

Although the thickness of a fluorine-containing film is selected according to an objective and a use, it does not specifically limit, The thing of 10-3000 micrometers is used, Preferably it is 20-500 micrometers, Especially preferably, it is 40-300 micrometers.

Too thin films require special manufacturing methods or are difficult to handle when carrying out an adhesive operation, which can easily cause wrinkles, breakage, and poor appearance, and they are insufficient in terms of adhesive strength, mechanical strength, chemical resistance, and weather resistance. There is a case. Too thick films are disadvantageous in terms of cost and workability when bonding and integrating.

In the present invention, the fluorine-containing polymer film may be used alone, or a fluorine-containing polymer formed by laminating a fluorine-containing ethylenic polymer film (adhesive layer) having the above-described functional group and a fluorine-containing ethylenic polymer film (surface layer) having no functional group. It may be applied in the form of a laminated film.

In other words, one side is provided with adhesiveness with another base material by the layer which consists of a functional group containing fluorine-containing ethylenic polymer, and the other side is made into the layer which consists of a general fluorine-containing polymer. The surface of the functional group-containing fluorinated ethylenic polymer is brought into contact with a substrate and bonded by thermocompression or the like, so that the excellent properties such as non-tackiness, antifouling property, low friction, weather resistance, chemical resistance, etc. It can give to a base material or the composite material containing a base material.

The thickness of the two-layer fluorine-containing polymer laminate film in the present invention is selected according to the purpose and use, and is not particularly limited, but the two layers are combined in a range of 20 to 5000 µm, preferably 40 to 1000 µm, particularly preferably Is 100-500 micrometers.

As for the thickness of each layer, the thing of about 5-1000 micrometers of adhesive layers and about 15-4995 micrometers of a fluorine-containing polymer layer (surface layer) can be used, Preferably an adhesive layer of 10-500 micrometers and a surface layer of 30-990 micrometers, Especially preferably, an adhesive layer 10-200 micrometers, and surface layers 90-490 micrometers.

Moreover, after sticking the film for adhesive layers to a base material, you may coat the film for surface layers.

In the functional group-containing fluorine-containing polymer film, an appropriate reinforcing agent, filler, stabilizer, ultraviolet absorber, pigment and other additives may be appropriately contained within a range that does not impair properties. By such an additive, it is also possible to improve the thermal stability, the surface hardness, the abrasion resistance, the weather resistance, the chargeability, and the like.

The fluorine-containing film in the present invention is coated with a thermal melting method, an extrusion method, a cutting method, a solvent casting, a powder, an aqueous or an organic solvent dispersion by the type of polymer used therein and the shape of the target film. It can be obtained by various manufacturing methods, such as a method of obtaining a film as a continuous film.

For example, the above-mentioned melt-molded polymer made of reactive PTFE can be molded by compression molding, extrusion molding (ram extrusion, paste extrusion, rolling processing, etc.), and reactive polymers such as reactive PFA, FEP, ETFE and the like. In the melt-molding polymer, compression molding, extrusion molding, and the like are employed, and melt extrusion molding is a preferred method especially for reasons of productivity and quality.

In other words, one side provides adhesiveness with another base material by the layer which consists of a functional group containing fluorine-containing ethylenic polymer, and the other side is made into a layer which consists of a general fluorine-containing polymer. The surface of the functional group-containing fluorinated ethylenic polymer is brought into contact with a substrate and bonded by thermocompression or the like to provide excellent chemical resistance, weather resistance, fouling resistance, non-adhesiveness, low friction, and electrical properties of the fluorinated polymer (high frequency electric Excellent properties such as insulation properties can be imparted to the base material or the composite material including the base material.

The thickness of the two-layer fluorine-containing polymer laminate film according to the present invention is selected according to the purpose and use, and is not particularly limited, but in combination with two layers, 20 to 5000 m, preferably 40 to 1000 m, particularly preferably 100-500 micrometers.

As for the thickness of each layer, the thing of about 5-1000 micrometers of adhesive layers and about 15-4995 micrometers of a fluorine-containing polymer layer (surface layer) can be used, Preferably an adhesive layer of 10-500 micrometers and a surface layer of 30-990 micrometers, Especially preferably, an adhesive layer 10-200 micrometers, and surface layers 90-490 micrometers.

Moreover, after sticking the film for adhesive layers to a base material, you may coat the film for surface layers.

In the functional group-containing fluorine-containing polymer film, it is also possible to contain suitable additives such as suitable reinforcing agents, fillers, stabilizers, ultraviolet absorbers, pigments and the like within a range not impairing properties. By such an additive, it is also possible to improve the thermal stability, the surface hardness, the abrasion resistance, the weather resistance, the chargeability, and the like.

The fluorine-containing resin film according to the present invention is coated with a thermal melting method, an extrusion method, a cutting method, a solvent casting, a powder, an aqueous or an organic solvent dispersion by the type of the polymer used therein and the shape of the target film. It can be obtained by various manufacturing methods, such as a method of obtaining a film as a post continuous film.

For example, the melt-molded polymer made of the above-mentioned reactive PTFE can be molded by compression molding, extrusion molding (ram extrusion, paste extrusion, rolling processing, etc.), and reactive PFA, FEP, ETFE and the like. Similarly, in the melt-molding polymer, compression molding, extrusion molding, and the like are employed, and melt extrusion molding is a preferred method for reasons such as productivity and quality.

Bonding integration of laminated films is achieved by overlapping and molding each of the molded films for the adhesive layer and the surface layer by compression molding, coating the other on one of the molded films, and multi-layer coextrusion molding. The method of achieving this etc. can be employ | adopted, and the multilayer coextrusion method is preferable especially from a viewpoint of productivity and quality.

Adhesion of the functional group-containing fluorine-containing polymer film to the substrate is achieved by thermal activation by heating or the like, and more preferably, hot melt adhesion is preferable. Representative bonding methods are the hot roll method, the hot press method, other high frequency heating methods, the micro method, the vacuum pressing method (vacuum press, etc.), the pneumatic method, and the like, depending on the type and shape of the substrate and the state and type of the film. We can choose appropriately.

As a base material with which the said functional group containing fluorine-containing ethylenic polymer can adhere | attach, a metal base material, a ceramic base material, and a resin base material are mentioned.

Metal-based metals include metal salts such as alloys, metal oxides, metal hydroxides, carbonates, and sulfates of metals and two or more metals. Among them, metals, metal oxides and alloys are more preferable in terms of adhesion.

Specific examples of the metal-based substrate include metals and metal compounds such as aluminum, iron, nickel, titanium, molybdenum, magnesium, manganese, copper, silver, lead, tin, chromium, beryllium, tungsten and cobalt, and alloys of two or more thereof. And the like.

Specific examples of the alloys include alloy steels such as carbon steel, Ni steel, Cr steel, Ni-Cr steel, Cr-Mo steel, stainless steel, silicon steel, and permalloy, Al-Cl, Al-Mg, Al-Si, Al Aluminum alloys such as -Cu-Ni-Mg, Al-Si-Cu-Ni-Mg, copper alloys such as brass, bronze (bronze), silicon bronze, silicon brass, german silver, nickel bronze, nickel manganese (D nickel) And nickel alloys such as nickel-aluminum (Z nickel), nickel-silicon, Monel metal, Constantan, nichrome inconel, Hastelloy and the like.

Moreover, about aluminum metal, pure aluminum, an oxide of aluminum, Al-Cu system, Al-Si system, Al-Mg system, Al-Cu-Ni-Mg system, Al-Si-Cu-Ni-Mg system alloy, Aluminum alloys for casting or telegraph such as high-strength aluminum alloys and corrosion-resistant aluminum alloys can be used.

In addition, as iron-based metals, pure iron, iron oxide, carbon steel, Ni steel, Cr steel, Ni-Cr steel, Cr-Mo steel, Ni-Cr-Mo steel, stainless steel, silicon steel, permalloy, non-magnetic steel (不 感 磁性)

Iii), magnetic steel, cast iron, or the like.

In order to prevent corrosion of metals, electroplating, hot-dip plating, chromizing, siliconizing, calorizing, shading, spraying, etc. are performed on the metal surface. To form another metal, to form a phosphate coating by phosphate treatment, to form a metal oxide by anodization or heat oxidation, or to adhere to a substrate subjected to electrochemical corrosion prevention.

Further, for the purpose of further improving the adhesion, the metal substrate surface may be subjected to chemical conversion treatment with phosphate, sulfuric acid, chromic acid, oxalic acid, or the like, or sandblasted, shot blasted, grit blasted, honed ( Surface roughening treatments such as honing), paper scratches, wire scratches, and hairline treatments may be carried out, and metallic surfaces may be colored, printed, or etched for the purpose of designability.

Further, in the case of the aluminum or aluminum alloy-based substrate, anodized with caustic soda, oxalic acid, sulfuric acid, and chromic acid is formed to form an oxide film on the surface thereof for the purpose of preventing corrosion, surface curing, and improving adhesion. What was made (alumite), and the surface treatment mentioned above can also be used.

 In addition, as described above, the other metal is plated on the surface, for example, hot dip galvanized steel sheet, alloyed hot dip galvanized steel sheet, aluminum plated steel sheet, zinc nickel plated steel sheet, zinc aluminum steel sheet, etc. A metal film may be formed, an oxide film may be formed by chemical conversion or heat treatment of chromic acid or phosphoric acid, or an electrical corrosion prevention method may be used (for example, a carbanic steel sheet).

As a ceramic base material, glass, a pottery, porcelain, etc. are mentioned, for example.

The glass is not particularly limited in composition, and examples thereof include quartz glass, lead glass, alkali free glass and alkali glass.

As a resin base material, an acrylic resin, polycarbonate, heat resistant engineering plastic, a thermosetting resin, etc. are mentioned, for example.

As a base material of the composite material for cooking appliances of this invention, as said metal base material among said base materials,

① cold rolled steel sheet,

② plated steel sheet, for example, Zn plated steel sheet or Zn alloy plated steel sheet, Al plated steel sheet or Al alloy plated steel sheet, Cr plated steel sheet (TFS), Ni plated steel sheet, Cu plated steel sheet, galvanized steel sheet, etc.

③ aluminum plate,

④ titanium plate,

⑤ stainless steel plate,

Etc. are normally used.

In addition, glass of ceramic base material, acrylic resin of resin base material, polycarbonate, etc. are used normally in the part where transparency is calculated | required.

Moreover, since processing may be difficult depending on the kind of cooking apparatus, it is preferable to make a base material into the shape of a final product.

In the composite material of the present invention, first, the fluorine-containing resin is applied to the substrate with good adhesiveness, and secondly, the fluorine-containing resin has good transparency (designability), heat resistance, non-adhesiveness, antifouling property, water and oil repellency, and the like. From having it, it can be used for various cooking appliances.

Suitable cooking apparatuses and parts thereof in which the composite for cooking apparatus of the present invention can be used are specifically listed below according to the field of cooking apparatus. Therefore, the present invention also relates to a cooking appliance and various parts described later.

Moreover, these were sorted and grouped for each item and shown in Tables 1-7.

① jar and port

(a) the inner surface and inner lid of electrical ports, including electric scrubbers;

In these, the antifouling property (to the scale), hot water resistance, and antibacterial property of the composite for cooking appliance of the present invention can be used particularly effectively.

(b) Inner lids and inner lids of gas and electric field cookers and rice cookers with rice washing equipment.

In these, the non-tackiness (for a grain of rice, a sticking) and heat resistance which the composite material for a cooking appliance of this invention has can be utilized especially effectively.

② Cooking Equipment

(a) Surfaces and bowls, such as frying pans, bats, cooking mixers for cooking and home use, colanders, knives, baker's moulds, baker's reverse seats, baker's split rounders, and inner surfaces such as rice arks, wings, etc. in the mixer. .

In these, the non-tackiness (for sticking and sticking), antifouling property, and heat resistance of the composite for cooking appliance of the present invention can be used particularly effectively.

(b) Inside and wings of electric food processors, such as household electric food grinders, electric food crushers, kitchen electric meat grinders, kitchen electric blenders and kitchen electric mixers.

In these, the non-tackiness (to vegetables and broth) and antifouling property of the composite for cooking appliance of the present invention can be used particularly effectively.

③ Gas table

(a) Top plates, sides, surfaces of gas stoves, such as gas cylinder-attached gas stoves, and surfaces of their sump lids;

In these, the non-tackiness (to oil dirt), heat resistance, and transparency (designability regarding color, shape, etc.) which the composite material for cooking appliances of this invention have can be used especially effectively.

④ Oven range including toaster, range

(a) Baking ovens, such as commercial ovens, electric ovens (including commercial use), electric ovens with commercial warmers, commercial cooking ovens, ovens for kitchen cooking stoves, kitchen baking ovens, automatic baking machines Electric oven toasters such as toasters, bread toasters, and inner surfaces of microwave ovens such as commercial microwave ovens, microwave ovens, and microwave ovens.

In these, the non-tackiness (to oil and sticking), antifouling property, and heat resistance which the composite material for cooking appliances of this invention have can be utilized especially effectively.

(b) Door inner surfaces of oven ranges listed in (a) above.

In these, in the case of the non-tackiness, heat resistance, transparency, and a microwave oven which the composite for cooking appliances of this invention have, the energy ray resistance can be utilized especially effectively.

⑤ Pots and Pots

(a) Inner surfaces of pots and pots such as glass pans, enamel pans, aluminum pans, electric frying pans, electric pressure pots and electric pressure stew pots.

In these, the non-tackiness (sticking, sticking, with respect to oil in the said frying pan) and heat resistance which the composite material for cooking appliances of this invention have can be utilized especially effectively.

(b) lids of pots and pots as described in (a) above;

In these, transparency other than the property of said (a) which the composite material for cooking appliances of this invention has can be used especially effectively.

⑥ Garbage Disposer

The inner surface of a cooking waste (waste) processor, such as a household cooking waste disposer and a composting device for food waste.

In these, the non-tackiness and antifouling property which the composite material for cooking appliances of this invention have can be utilized especially effectively.

⑦ Other heating cooking equipment

(a) Heating surface and lid of hot plate.

In these, the non-tackiness (for sticking and sticking), the heat resistance and the lid of the composite for cooking appliance of the present invention can be used particularly effectively.

(b) Cooking surfaces of microwave ovens, microwave ovens, etc.

In these, the non-tackiness, heat resistance, and transparency which the composite material for cooking appliances of this invention have can be utilized especially effectively.

(c) Inner surface, door inner surface and lid of electric steamer such as food steam for business.

In these, the non-tackiness, antifouling property, heat resistance, and steam resistance which the composite material for cooking appliances of this invention have can be utilized especially effectively.

(d) The inside and lid of commercial noodle cookers.

In these, the non-tackiness, antifouling property, heat resistance, and hot water resistance which the composite material for cooking appliances of this invention have can be utilized especially effectively.

(e) Inside, inside (metal parts), doors and range pans for commercial cookers.

In these, the non-tackiness (for sticking and sticking) and heat resistance which the composite material for a cooking appliance of the present invention has can be used particularly effectively.

(f) the inside of commercial dishwashers, canned washing machines, etc .;

In these, the non-tackiness, antifouling property, and heat resistance which the composite material for cooking appliances of this invention have can be utilized especially effectively.

(g) Internal surfaces of doors and doors for commercial warmers.

In these, the non-tackiness, antifouling property, transparency, and heat resistance which the composite material for cooking appliances of this invention have can be utilized especially effectively.

Moreover, the following are mentioned as a cooking appliance of that excepting the above which can apply the composite material for cooking appliances of this invention preferably.

As a thing of the said ① (b), a rice cooker, a warm rice cooker, etc.

In the range of ② (a) above, various cooking utensils (for cutting, etc.), cooking utensils, cooking utensils, cooking apparatus (for food, etc.), cooking iron plate, cooking utensils and equipment, barbecue utensils, Food processing machinery (with pressure device, etc.), chocolate makers, and temperature control mechanisms for processing raw materials.

In the range of ② (b) above, a synthetic cooker, a vegetable slicer, a food slicer, a bloomer, a dice cutter, a food cutter, a meat chopper, a meat slicer, a meat tenderizer, a cutter mixer, a mixer, a food mixer, a blender, an apple cooker , Continuous egg machine, tofu cutting food forming machine, bread crumb attacher, vegetable washing machine, etc.

Low ranges, table stoves, electric ranges, gas ranges, gas tables, electric tables and the like in the above range.

Gas salamanders, electric salamanders, convection ovens, baking furnaces, and the like, as in the above ranges.

As the above-mentioned (5), a neutralization pot, a one-handed pot, a two-handed pot, a gas fryer, a frying fryer, an oil filter unit, a wheat pot, a rotating pot, and the like.

Grilled dumplings, a microwave oven, a gas steamer, a steam steamer, etc. in the range of said 7 ,.

Example

Preparation Example 1

(Production of Aqueous Acid Acid Consisting of PFA Having a hydroxyl Group)

Into a 3-liter glass-lined autoclave equipped with a stirrer, a valve, a pressure gauge, and a thermometer, 1500 ml of pure water and 9.0 g of ammonium perfluorooctanoate were added, followed by sufficient replacement with nitrogen gas, followed by vacuum to 20 ml of ethane gas. Put it.

Perfluoro (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol) (Formula (7))

3.8 g of and 18 g of perfluoro (propyl vinyl ether) (PPVE) were press-fitted using nitrogen gas, and the temperature in the system was kept at 70 ° C.

While stirring, tetrafluoroethylene gas (TFE) was press-fitted so that internal pressure might be 8.5 kgf / cm <2> G.

Subsequently, the solution which melt | dissolved 0.15 g of ammonium persulfate in 5.0 g of water was indented using nitrogen, and reaction was started.

Since the pressure lowered as the polymerization proceeded, the pressure was reduced to 8.5 kgf / cm 2 with tetrafluoroethylene gas at the time when the pressure was reduced to 7.5 kgf / cm 2 G, and the step-down and the step-up were repeated.

When the tetrafluoroethylene gas is consumed by about 40 g from the start of the polymerization while supplying the tetrafluoroethylene, 1.9 of the fluorine-containing ethylenic monomer having the hydroxyl group (compound represented by the formula (7) above) The polymerization was continued by injecting g a total of 3 times (total 5.7 g), and at the time when the polymerization was consumed, about 160 g of tetrafluoroethylene was stopped, the autoclave was cooled, the unreacted monomer was released, 1702 g of a translucent aqueous acidic acid which was started was obtained.

The particle diameter measured by the concentration of the polymer in the obtained aqueous component was 10.9% and the dynamic light scattering method was 70.7 nm.

A part of the obtained aqueous acidic acid was taken, and freeze coagulation was carried out. The precipitated polymer was washed and dried to isolate a white solid. The composition of the obtained copolymer was TFE / PPVE / (fluorine-containing ethylenic monomer having a hydroxyl group represented by formula (7)) = 97.7 / 1.2 / 1.1 mol% by ¹⁹ F-NMR analysis and IR analysis.

In addition, the absorption characteristics of -OH were observed in the infrared spectrum at 3620-3400 cm ^-1 .

By DSC analysis, Tm = 310 degreeC and 1% pyrolysis temperature Td = 368 degreeC by DTGA analysis. Melt flow rate was measured at a load of 7 kgf / cm 2 for 5 minutes preheated at 372 ° C using a nozzle of 2 mm and 8 mm in length using a solid flow tester. / 10 minutes.

Preparation Example 2

(Production of Aqueous Acid Acid Consisting of PFA Having a hydroxyl Group)

1500 ml of pure water and 9.0 g of ammonium perfluorooctanoate were added to the same autoclave as in Preparation Example 1, and the resulting mixture was sufficiently replaced with nitrogen gas, and 20 ml of ethane gas was added under vacuum.

Then 1.9 g of perfluoro (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol) (compound of formula (7)), 16.1 g of perfluoro (propyl vinyl ether) (PPVE) was press-fitted using nitrogen gas to maintain the temperature in the system at 70 ° C.

While stirring, tetrafluoroethylene (TFE) was press-fitted to internal pressure 8.5 kgf / cm <2> G.

Subsequently, the solution which melt | dissolved 0.15 g of ammonium persulfate in 5.0 g of water was indented using nitrogen, and reaction was started.

Since the pressure lowered as the polymerization proceeded, the pressure was lowered to 7.5 kgf / cm 2 G and re-pressurized to 8.5 kgf / cm 2 G with tetrafluoroethylene gas.

0.95 g of the fluorine-containing ethylenic monomer (compound represented by the formula (7)) having the hydroxyl group described above is consumed every time about 40 g of tetrafluoroethylene gas is consumed from the start of the polymerization while the supply of tetrafluoroethylene is continued. The polymerization was continued by injecting a total of 3 times (2.85 g in total), and the supply was stopped when 160 g of tetrafluoroethylene was consumed from the start of polymerization, and the autoclave was cooled to release unreacted monomer. 1692 g of aqueous acids were obtained. The polymer concentration in the obtained aqueous dispersion was 10.6% and the particle diameter was 76.8 nm.

In the same manner as in Production Example 1, a part of the aqueous component was extracted to isolate a white solid.

As a result of analyzing the white solid obtained by the same method, TFE / PPVE / (fluorine-containing monomer having a hydroxyl group of formula (7)) = 98.3 / 1.1 / 0.6 mol%,

Tm = 310 ° C,

1% pyrolysis temperature Td = 374 ℃,

Melt flow rate: 9.5 g / 10 min,

In addition, the absorption characteristics of -OH were observed in the infrared spectrum at 3620-3400 cm ^-1 .

Preparation Example 3

(Synthesis of Aqueous Acid Acid of PFA without Functional Group)

In Preparation Example 1, perfluoro (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol) (Compound represented by formula (7) Except not using), emulsion polymerization was carried out in the same manner as in Production Example 1 to obtain 1662 g of an aqueous acidic acid component of PFA containing no functional group.

The polymer concentration in the aqueous component was 9.7% and the particle diameter was 115 nm.

In the same manner as in Preparation Example 1, the white solid was isolated and analyzed.

TFE / PPVE = 98.9 / 1.1 mol%

Tm = 310 ° C,

1% pyrolysis temperature Td = 479 ℃,

Melt flow rate: 19.2 g / 10 min,

In addition, no characteristic absorption of -OH was observed in the infrared spectrum.

Preparation Example 4

(Synthesis of PFA having a hydroxyl group)

Into a 6-liter glass-lined autoclave equipped with a stirrer, a valve, a pressure gauge and a thermometer, 1500 ml of pure water was sufficiently substituted with nitrogen gas, and then vacuumed to provide 1,2-dichloro-1,1,2 1500 g of, 2-tetrafluoroethane (R-114) was added thereto.

Next, perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol) (compound represented by formula (7)) 5.0 g, 130 g of perfluoro (propyl vinyl ether) (PPVE), and 180 g of methanol were press-fitted using nitrogen gas to maintain the temperature in the system at 35 ° C.

While stirring, tetrafluoroethylene gas (TFE) was press-fitted so that internal pressure might be 8.0 kgf / cm <2> G. Subsequently, 0.5 g of a 50% methanol solution of di-n-propylperoxydicarbonate was pressed with nitrogen to initiate a reaction.

Since the pressure lowered as the polymerization proceeded, the pressure was reduced to 8.0 kgf / cm 2 with tetrafluoroethylene gas at the time when the pressure dropped to 7.5 kgf / cm 2 G, and the step-down and the step-up were repeated.

When the tetrafluoroethylene gas is consumed at about 60 g from the start of the polymerization while supplying the tetrafluoroethylene, 2.5 of the fluorine-containing ethylenic monomer having the hydroxyl group (compound represented by the formula (7) above) The polymerization was continued by injecting g a total of 9 times (22.5 g in total), and the feed was stopped at the time when about 600 g of tetrafluoroethylene was consumed from the start of the polymerization, and the autoclave was cooled to remove unreacted monomer and R-114. Released.

After washing the obtained copolymer with water and washing with methanol, 710 g of a white solid was obtained by vacuum drying. The composition of the obtained copolymer was TFE / PPVE / (fluorine-containing ethylenic monomer having a hydroxyl group represented by formula (7)) = 97.0 / 2.0 / 1.0 mol% by 19F-NMR analysis and IR analysis. Moreover, the infrared absorption showed the characteristic absorption of -OH in 3620-3400 cm <^-1> . By DSC analysis, Tm was 305 ° C and 1% pyrolysis temperature Td was 375 ° C by DTGA analysis. It was 32 g / 10min when the melt flow rate was measured by the load of 7 kgf / cm <2> for 5 minutes of preheating at 372 degreeC using the nozzle of diameter 2mm and length 8mm using the solidified flow tester.

Preparation Example 5

(Synthesis of PFA having a hydroxyl group)

Into a 6-liter glass-lined autoclave equipped with a stirrer, a valve, a pressure gauge and a thermometer, 1500 ml of pure water was sufficiently substituted with nitrogen gas, and then vacuumed to provide 1,2-dichloro-1,1,2 1500 g of, 2-tetrafluoroethane (R-114) was added thereto.

Then 2.5 g of perfluoro- (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol) (formula (7)), Reaction was initiated in the same manner as in Production Example 4 except that 132 g of perfluoro (propyl vinyl ether) (PPVE) and 230 g of methanol were used, and the temperature was maintained at 35 ° C.

While stirring, tetrafluoroethylene gas (TFE) was press-fitted so that internal pressure might be 8.0 kgf / cm <2> G. Subsequently, 0.5 g of a 50% methanol solution of di-n-propylperoxydicarbonate was indented using nitrogen to initiate a reaction.

Since the pressure lowered as the polymerization proceeded, the pressure was reduced to 8.0 kgf / cm 2 with tetrafluoroethylene gas at the time when the pressure dropped to 7.5 kgf / cm 2 G, and the step-down and the step-up were repeated.

In addition, the amount of the fluorine-containing ethylenic polymer (compound represented by the above formula (7)) having the hydroxyl group indented every time about 60 g of tetrafluoroethylene gas was consumed from the start of polymerization was 9 times in total. A white solid of 680 g of a copolymer was obtained in the same manner as in Production Example 4, except that the total amount was 11.10 g. The composition of the obtained copolymer was TFE / PPVE / (fluorine-containing ethylenic monomer having a hydroxyl group represented by formula (7)) = 97.6 / 2.0 / 0.4 mol% by ¹⁹ F-NMR analysis and IR analysis. Moreover, the infrared absorption showed the characteristic absorption of -OH in 3620-3400 cm <^-1> . By DSC analysis, the decomposition start temperature was 368 ° C and 1% pyrolysis temperature Td = 375 ° C by Tm = 310 ° C and DTGA analysis. It was 42 g / 10min when the melt flow rate was measured by the load of 7 kgf / cm <2> for 5 minutes of preheating at 372 degreeC using the nozzle of diameter 2mm and length 8mm using the solidified flow tester.

Preparation Example 6

(Synthesis of PFA containing no functional group)

Perfluoro (1,1,9,9-tetrahydro-2,5-bistrifluoromethyl-3,6-dioxa-8-nonenol) according to Production Example 4 shown by Formula (7) The compound was synthesized in the same manner as in Production Example 4, except that 240 g of methanol was not used, and PFA 597 g containing no functional group was obtained.

As a result of analyzing PFA obtained by the same method as Preparation Example 4,

TFE / PPVE = 98.2 / 1.8 mol%

Tm = 310 ° C,

Td = 469 ° C (1% weight loss),

Melt flow rate = 24 g / 10 minutes

It was.

Preparation Example 7

(Production of PFA Powder Coating Having a hydroxyl Group)

PFA powder having a hydroxyl group obtained in Production Example 4 (appearance specific gravity 0.5, true specific gravity 2.1, average particle diameter 600 microns) by a roller compactor (Shintokyo Kogyo Co., Ltd. type BCS-25 type) width 60 mm, thickness 5 It compressed to the sheet form at mm. Next, it grind | pulverized to about 10 mm diameter, and it grind | pulverized again at 11000 rpm at room temperature using the grinder (Cosmo-Miser-N-1 type | mold by Narakai Co., Ltd.). Next, a coarse molecule of 170 mesh (88 micron mesh scale) or more was removed with a classifier (Hinboder-300SD type manufactured by Shindo Pure Chemical Industries, Ltd.) to obtain a PFA powder coating having a hydroxyl group. The apparent density of the powder was 0.7 g / ml and the average particle diameter was 20 µm.

Preparation Example 8

(Production of PFA Powder Coating without Functional Group)

The same method as in Preparation Example 7 except for using the PFA powder containing no functional group (Appearance Ratio 0.6, Grain Ratio 2.1, Average particle size 400 microns) instead of the PFA powder having a hydroxyl group obtained in Preparation Example 4. PFA powder coating was made. The apparent density of the powder was 0.73 g / ml and the average particle diameter was 20 µm.

Preparation Example 9

(Synthesis of Fluorinated Polymer Using Functional Group-containing Monomer without Fluorine)

In a 1 liter stainless steel autoclave equipped with a stirrer, a valve, a pressure gauge and a thermometer, 250 g of butyl acetate, 36.4 g of vinylic acid vinyl (PPi), a hydroxyl group-containing monomer containing no fluorine, 4 32.5 g of hydroxyl butyl vinyl ether (HBVE) and 4.0 g of isopropoxycarbonyl peroxide were added thereto, and the mixture was cooled with ice to 0 ° C., sufficiently substituted with nitrogen gas, and vacuumed to obtain 47.5 g of isobutylene (IB); 142 g of tetrafluoroethylene (TFE) was added.

It heated at 40 degreeC, stirring, and made it react for 30 hours, and stopped reaction at the time when the pressure in a reaction container fell to 2.0 kg / cm <2> or less. When the autoclave was cooled and the unreacted gas monomer was released, a butyl acetate solution of a fluorine-containing polymer was obtained. The polymer concentration was 45%.

From the butyl acetate solution of the obtained fluorine-containing polymer, the fluorine-containing polymer was extracted by the reprecipitation method, and isolated as a white solid by fully depressurizing and drying. ^The fluorine-containing polymer obtained by ¹ H-NMR and ¹⁹ F-NMR elemental analysis was analyzed and found to be a copolymer consisting of TFE / IB / VPi / HBVE = 44/34/15/7 mol.

Preparation Example 10

(Production of a film of PFA having a hydroxyl group)

8.0 g of the white solid obtained in Production Example 4 was placed in a 100 mmφ mold and placed in a press set at 350 ° C. for preheating for 30 minutes, followed by compression molding at 70 kg / cm 2 for 1 minute, and a film having a thickness of 0.5 mm. Got.

Preparation Example 11

(Production of a film of PFA having a hydroxyl group)

A film having a thickness of 0.5 mm was obtained in the same manner as in Production Example 10, except that the white solid obtained in Production Example 5 was used.

Preparation Example 12

(Preparation of PFA film containing no functional group)

A film having a thickness of 0.5 mm was obtained in the same manner as in Production Example 10, except that the white solid obtained in Production Example 6 was used.

Preparation Example 13

(Production of Film by Extrusion of PFA Having a hydroxyl Group)

From the white solid obtained in the manufacture example 4, the pellet was produced by extrusion at 350-370 degreeC using the twin screw extruder (Labo Plasma mill manufactured by Toyo Seiki Co., Ltd.). Using the pellet, extrusion was carried out at 360 ° C to 380 ° C and a roll temperature of 120 ° C with a single screw extruder (Labo Plasma Mill manufactured by Toyo Seiki Co., Ltd.) to obtain a film having a width of 10 cm and a thickness of 100 to 150 m. Got it.

Preparation Example 14

(Preparation of film by PFA extrusion without functional group)

A pellet was produced in the same manner as in Production Example 13 except that the white solid obtained in Production Example 6 was used. Then, extrusion was carried out to obtain a width of 10 cm and a thickness of 100 to 150 µm in the same manner as in Production Example 17.

Preparation Example 15

(Laminated film of PFA having a hydroxyl group and PTFE)

The PFA film having the hydroxyl group obtained in Production Example 13 and the PTFE film having a thickness of 0.5 mm were overlapped and compression molded in the same manner as in Production Example 10.

The two layers were firmly bonded to each other.

Example 1

(1) pretreatment of substrate

Degreasing was performed with acetone, respectively, using pure aluminum plate (A1050P) of thickness 1.5mm and SUS304 of thickness 1.5mm.

(2) Formation of primer layer composed of fluorine-containing polymer having functional group

Using an aqueous dispersion composed of PFA having a hydroxyl group obtained in Production Example 1, the film was coated with an air spray so as to have a thickness of about 5 μm, infrared dried at 90 ° C. for 10 minutes, and then calcined at 380 ° C. for 20 minutes. .

(3) Formation of layer (upper layer) made of fluorine-containing polymer having no functional group

A coating made of a fluorine-containing polymer having no functional group on the primer layer obtained in (2), wherein the aqueous coating made of PTFE (polypropylene TFE enamel EK4300CRN manufactured by Diking Co., Ltd.) is about 20 μm in thickness by air spray. It coated so that it might become, and it infrared-dried at 90 degreeC for 10 minutes, and baked at 380 degreeC for 20 minutes.

(4) evaluation of adhesion

The evaluation method is as follows.

(Checker scale test)

100 masses of checkerboard scales specified in JIS K 5400 1990, 8.5.2 are made on the coated surface, and a cello tape (adhesive tape manufactured by Nichibang Co., Ltd.) is sufficiently adhered to this surface and immediately removed. This detachment is performed 10 times with a new cello tape to evaluate how many of the 100 masses remain. The results are shown in Table 8.

Example 2

A plate was produced in the same manner as in Example 1, except that the primer layer was formed of the primer composed of the PFA having the hydroxyl group obtained in Production Example 2 with the primer made of the fluorine-containing polymer having a functional group. Evaluation of adhesiveness was performed. The results are shown in Table 8.

Comparative Example 1

A plate was produced in the same manner as in Example 1, except that a primer layer was formed using an aqueous acid composition consisting of PFA without a functional group obtained in Production Example 3, instead of a primer made of a fluorine-containing polymer having a functional group. Evaluation of adhesiveness was performed. The results are shown in Table 8.

Examples 3, 4 and Comparative Example 2

Example 3 is an example except that the upper layer was formed using a water-based coating made of FEP (neopron FEP dispersion ND-1 manufactured by Daison Kogyo Co., Ltd.) as a paint made of a fluorine-containing polymer having no functional group. In Example 1 and Example 4, Example 2 and Comparative Example 2 were each prepared in the same manner as in Comparative Example 1 to evaluate the adhesion. The results are shown in Table 8.

Example 5

(1) pretreatment of substrate

It carried out by the same method as Example 1.

(2) Formation of a primer layer made of a fluorine-containing polymer having a functional group

The aqueous component consisting of PFA having a hydroxyl group obtained in Production Example 1 was coated with an air spray so as to have a thickness of about 5 μm, and infrared dried at 90 ° C. for 10 minutes.

(3) Formation of a layer (upper layer) made of a fluorine-containing polymer having no functional group

As a coating material which consists of a fluorine-containing polymer which does not have a functional group on the primer layer obtained by said (2), by electrostatic coating using the powder coating of PFA (neopron PFA powder coating ACX-31 by Daiseng Kogyo Co., Ltd.). And coating was carried out so that the film thickness was 40 µm, and calcined at 380 ° C. for 20 minutes.

(4) evaluation of adhesion

It carried out by the same method as Example 1. The results are shown in Table 8.

Example 6

A plate was produced in the same manner as in Example 5 except that the primer layer formed of the primer composed of the PFA having the hydroxyl group obtained in Production Example 2 was made of the primer made of the fluorinated polymer having the functional group. Evaluation of adhesiveness was performed. The results are shown in Table 8.

Comparative Example 3

Instead of a primer made of a fluorine-containing polymer having a functional group, except that a primer layer was formed by using an aqueous acid body composed of PFA having no functional group obtained in Preparation Example 3, a plate was produced and bonded in the same manner as in Example 5. Sex evaluation was performed. The results are shown in Table 8.

Example 7

(Evaluation of Adhesiveness of PFA Powder Coatings Having a hydroxyl Group)

(1) Preparation of press sheet for adhesion test

About 4 g of PFA powder coating having a hydroxyl group obtained in Production Example 7 was put into a cylindrical mold having a diameter of 60 mm, and compression molded at a pressure of 300 kgf / cm 2 at room temperature using a press machine to form a disc shaped cold press (hereinafter, Also called "PFA sheet").

(2) substrate pretreatment

After degreasing 100 x 100 x 1 (mm) pure aluminum plate with acetone, sandblasting was performed.

(3) adhesive sample manufacturing

The PFA sheet obtained in the above (1) was placed on an aluminum plate (above (2)), placed in a hot air dryer, and heated and melted at 330 ° C for 10 minutes. The sample which the film thickness about 450 micrometers PFA sheet adhere | attached on the aluminum plate was obtained. The schematic plan view of the adhesive sample which consists of a PFA sheet 1 and the aluminum plate 2 is shown in FIG.

(4) Measurement of adhesive strength

As shown in Fig. 1, a sheath is cut into the PFA sheet 1 of the adhesive sample obtained in the above (3) with a cutter at intervals of width (a; 10 mm), and one end of each rectangular sheet 1 is removed. It bent and the measuring mechanism for adhesive strength measurement was obtained. The schematic perspective view of the measuring mechanism for adhesion | attachment measurement obtained in FIG. As shown in FIG. 2, the sheet | seat 1 was pulled at the angle of 90 degrees with respect to the aluminum plate 2, and peeling strength was measured. Using Tensileron Universal Testing Machine (manufactured by Orien Tech Co., Ltd.) at room temperature, the crosshead speed was measured at 50 mm / min, and the adhesive strength of 5.5 kgf / cm was shown at the average peeling load by the area method.

Comparative Example 4

(Evaluation of Adhesiveness of PFA Powder Coating without Functional Group)

In the same manner as in Example 7 except that the PFA powder coating containing no functional group was used instead of the PFA powder coating having a hydroxyl group obtained in Preparation Example 7, the preparation of the adhesion test press sheet, the pretreatment of the substrate, An adhesive sample was prepared to measure the adhesive strength.

The adhesive strength of the PFA powder coating containing no functional group was 0.8 kgf / cm.

Example 8

(Electrostatic coating of PFA powder coating having hydroxyl group)

PFA powder coating having a hydroxyl group obtained in Production Example 7 was applied to an aluminum plate pretreated in the same manner as in Example 7, using an electrostatic powder coating machine (type GX3300 manufactured by Iwata Doso Co., Ltd.) at room temperature. The electrostatic coating was carried out at a voltage of 40 kV. The coating plate was baked at 330 ° C. for 15 minutes with a hot air dryer to obtain a coating film.

The coating film was a transparent and uniform continuous film, and all the base aluminum plates were firmly in contact with each other.

Comparative Example 5

(Heat resistance of fluorine-containing polymer using functional group-containing monomer without fluorine)

The pyrolysis temperature of the fluorine-containing polymer obtained in Production Example 9 was measured by TGA analysis, and it was 220 ° C at 1% pyrolysis temperature. From this, it was found that the fluorine-containing polymer using the functional group-containing monomer having no fluorine as obtained in Production Example 9 was low in heat resistance.

Further, the fluorine-containing copolymer obtained in Production Example 9 was dissolved in butyl acetate at a concentration of 10% by weight.

In the same manner as in Example 5, except that the butyl acetate solution of the fluorine-containing copolymer of Preparation Example 9 was used instead of the aqueous component of PFA having a hydroxyl group used in the primer layer. Pretreatment of the base material with the aluminum base material, application of the primer layer using the fluorinated copolymer of Preparation Example 9, and application of the upper layer (electrostatic coating of PFA powder coating) were performed.

After coating, the coating film obtained by baking for 20 minutes at 380 degreeC was colored yellowish brown, foaming and peeling were also seen, and the uniform transparent film was not obtained.

Examples 9-12

(Adhesion test between hydroxyl group-containing PFA film and metal)

As a metal plate, the adhesion test with the PFA film (film of manufacture example 10 or 11) which has a hydroxyl group was performed using the degreasing chromic acid, processed aluminum, pure aluminum, and steel plate of thickness 0.5mm as follows. The results are shown in Table 9.

(Production of test piece for peeling test)

The schematic perspective view of the laminated body produced in order to produce the test piece for peeling test in FIG. 3 is shown. As shown in FIG. 3, the hydroxyl group containing PFA film obtained by manufacture examples 10-11 was used as the adhesive bond layer 3, The spacer (aluminum foil; 4) of thickness 0.1mm was sandwiched between two metal plates 5, respectively. It set in the press set to 350 degreeC, preheated (20 minutes), pressurized at 50 kg / cm <2> for 1 minute, and obtained the laminated body of length (b; 150 mm) and width (c; 70 mm).

The thickness of the layer of the adhesive bond layer 3 of the obtained laminated body was all 0.1 mm. Moreover, the laminated body was cut | disconnected to width 25mm, and the spacer part was bent in T shape at the place (e; 100mm) from one end, and it was set as the test piece for peeling tests. The schematic perspective view of the test piece for peeling tests obtained in FIG. 4 is shown. In FIG. 4, 3 is an adhesive bond layer, and 5 is a metal plate.

(Peel test)

Based on the T-type peeling test method of JIS K6854-1977, it measured at 50 mm / min of crosshead speed at room temperature using the Tenshiron universal testing machine by Orient Tech Co., Ltd. product. The measurements showed the maximum peel strength (kgf / 25 mm) and the minimum peel strength (kgf / 25 mm).

Comparative Examples 6 to 8

(Adhesion test of metal with PFA film containing no functional group)

Preparation and peeling test of the test piece were performed by the method similar to Example 9 except having used the PFA film which does not contain the functional group obtained in manufacture example 12 instead of the PFA film which has the hydroxyl group of manufacture example 10 or 11. The results are shown in Table 9.

Examples 13-14

(Adhesion test between hydroxyl group-containing PFA film and glass)

Using 30 x 20 x 5 mm Pyrex glass as the glass plate, the adhesion test with PFA having a hydroxyl group was performed as follows.

In addition, a hot water resistance test and a methanol dipping test of the laminate after adhesion were also carried out. The results are shown in Table 10.

(Production of test piece for tensile shear test)

5 is a schematic perspective view of a test piece for tensile shear test. As shown in Fig. 5, the hydroxyl group-containing PFA film obtained in Production Examples 10 to 11 (length (f) was 10 m, width (g) was 20 mm, thickness (h) was 0.1 mm) was used as adhesive layer (3). As a Pyrex glass plate 6 (length (i) is 30 m, width (g) is 20 mm, thickness (j) is 5 mm), the load of 3 kg is raised, and 350 ° C and 30 in an electric furnace It left for a minute and obtained the test piece. The thickness of the adhesive bond layer 3 was adjusted to 0.1 mm with the spacer.

(Adhesive strength)

6 is a schematic explanatory diagram for explaining a test apparatus used for measuring the adhesive strength by the tensile shear method. As shown in FIG. 6, the test jig 8 matched with the shape of the test piece 7 obtained by the method as described above is set in Tensilon Universal Testing Machine 9 manufactured by Orient Tech Co., Ltd., and the crosshead speed 20 Tensile shear tests were performed at mm / min. The measurement showed the maximum adhesive strength (kgf / cm 2).

(Heat resistance test)

The test piece produced by the method shown above was immersed in 50 degreeC warm water, the adhesiveness after 6 hours was observed, and the adhesive strength (kgf / cm <2>) after 72 hours was measured.

(Methanol Dipping Test)

Adhesiveness was observed by immersing in methanol at room temperature using the test piece produced by the method shown above.

Comparative Example 9

(Adhesion of glass with PFA film containing no functional group)

The test piece was produced and various tests were carried out in the same manner as in Example 13 except that the PFA film containing no functional group obtained in Production Example 12 was used instead of the PFA film having hydroxyl groups of Production Example 10 or 11. The results are shown in Table 10.

Preparation Example 15

(Adhesion between hydroxyl group-containing PFA film and stainless steel, post processing test)

As a metal plate, the laminated test plate was manufactured by the following method using the degreasing SUS 304 steel plate of length 150mm, width 70mm, and thickness 0.5mm. The PFA film containing the hydroxyl group obtained in Production Example 13 and the PFA film containing no functional group obtained in Production Example 14 were cut to the same size as the SUS plate.

In addition, a polyimide film (Kapton 200-H manufactured by DuPont) was also cut to the same size as the peeling film.

The schematic sectional drawing of the laminated test board obtained in FIG. 7 is shown. As illustrated in FIG. 7, the hydroxyl group-containing PFA film 12, the PFA film 13 containing no functional group, and the polyimide film 14 were sandwiched between the two SUS plates 11, 350. It was set in the press set to ° C, preheated (20 minutes), and then pressurized at 50 kg / cm 2 for 1 minute to obtain a laminate test plate.

After cooling, the SUS plate 11 in contact with the polyimide film 14 was removed, and the polyimide film was naturally peeled off at the interface of the PFA film 14 containing no functional group.

As a result, a three-layered laminate of SUS plate 11 having good transparency and PFA film 13 having a hydroxyl group-containing PFA film 12 as an adhesive layer was obtained. The schematic sectional drawing of the obtained 3-layer laminated body is shown in FIG.

In addition, 100 pieces of checkerboard scales of 1 mm were made in the obtained three-layered laminate up to the SUS plate 1 based on the cutting knife, and the center of the checkerboard scale was pushed 5 mm by an Ericsen tester. As a result, the hydroxyl group-containing PFA film 12 did not peel at all and was firmly adhered to the SUS plate 11 serving as the base.

The PFA film 12 showed firm adhesiveness to the SUS plate 11.

Comparative Example 10

(Adhesion and post-processing test of PFA film not containing functional group and stainless steel)

Except not using the PFA film which has a hydroxyl group, the laminated body of the SUS board 11 and the PFA film 13 which does not contain a functional group was obtained by the method similar to Example 15. The schematic sectional drawing of the laminated body obtained in FIG. 9 is shown.

Although the obtained laminated body adhere | attached visually, the PFA film 13 which does not contain a functional group was able to be easily peeled from the SUS board 11.

In addition, the Ericsen test was implemented similarly to Example 15. In 60 of the checkerboard scales, 60 were peeled off around the sheath.

Example 16

(Adhesion test between hydroxyl group-containing PFA film and polyimide film)

The hydroxyl group-containing PFA film 12 obtained in Production Example 13, the PFA film 13 and polyimide film 14 containing no functional group obtained in Production Example 14 were cut to the same size as in Example 15, It sandwiched between SUS plates 11, and it heated in the press with the method similar to Example 15, and obtained the laminate test board. The schematic sectional drawing of the laminated test board obtained in FIG. 10 is shown. Next, after cooling, the SUS plate 11 was removed to obtain a laminate. The schematic sectional drawing of the laminated body obtained in FIG. 11 is shown. Moreover, the laminated body was cut | disconnected to width 25mm.

12, the schematic sectional drawing of the said laminated body used for T-type peeling test is shown. In FIG. 12, a part of the interface between the polyimide film 14 and the hydroxyl group-containing PFA film 12 was removed, and the T-type peeling test was performed in the same direction as in Example 1 in the arrow direction shown in FIG. 12. The adhesiveness of 4.0 kgf / 25mm was shown by the average peeling load by the method.

Comparative Example 11

(Adhesion test between PFA film containing no functional group and polyimide film)

The schematic sectional drawing of the laminated body used for a T-type peeling test by the method similar to Example 1 in FIG. 13 is shown. In FIG. 13, Example 16 was removed in the direction of the arrow shown in FIG. 13 by partially removing the interface between the polyimide film 14 of the laminate having a width of 25 mm obtained in Example 16 and the PFA film 13 containing no functional group. T-type peeling test was carried out in the same manner, but did not show adhesion.

Comparative Example 12

(Heat resistance of fluorine-containing polymer using functional group-containing monomer without fluorine)

The pyrolysis temperature of the fluorine-containing polymer obtained in Preparation Example 9 was 220 ° C. at 1% pyrolysis temperature, as determined by TGA analysis. From this, it was found that the fluorine-containing polymer using the functional group-containing monomer not having fluorine as obtained in Production Example 9 was low in heat resistance.

Further, the fluorinated polymer obtained in Production Example 9 was dissolved in butyl acetate at a concentration of 10% by weight.

The butyl acetate solution of the fluorine-containing polymer of Preparation Example 9 was coated on an aluminum plate subjected to the same pretreatment as in Example 9 with an air spray so as to have a film thickness of about 10 μm, and infrared dried at 90 ° C. for 10 minutes.

On the film 16 of the fluorine-containing polymer using the functional group-containing monomer not containing fluorine obtained by coating, the PFA film 13 without the functional group obtained in Production Example 14, the polyimide film 14 for mold release (Production Example Same as 15), the aluminum plate 15 was laminated in this order, and it heated and pressed at 350 degreeC with the same press machine as Example 15, and obtained the laminate test board. The schematic sectional drawing of the obtained laminated test board was shown in FIG.

After cooling this laminate test plate, the aluminum plate 15 and the polyimide film 14 which contact | connect the polyimide film 14 were removed, and the laminated body was obtained.

The obtained laminated body was colored yellowish brown, foaming, peeling, etc. also generate | occur | produced between the PFA film 13 and the aluminum plate 15, and the uniform and transparent laminated body was not obtained.

Examples 17-18

The coating plate electrostatically coated with the PFA powder coating having a hydroxyl group obtained in Example 8 (Example 17) and the extruded film of PFA having a hydroxyl group obtained in Production Example 13 (Example 18) were used as test plates. A non-tack test was performed by the method shown. The results are shown in Table 11.

(Non-tackiness Test)

The measurement was performed at 23 degreeC +/- 2 degreeC. The schematic perspective view of the test piece used for the non-adhesive test was shown in FIG. The test plate 17 was 150 mm or more in length, and the surface dirt was wiped off with acetone. First, the adhesive tape 18 (JIS Z1522) of 18 mm width is cut out 300 mm, and the length k part of 150 mm is put on the test board 17, and it rubs with the eraser of JIS S 6050 from the tape 18. And the bonding portion 19 are obtained by pressing. Paper was attached to the remaining 150 mm portion (not shown) to facilitate handling. It left for 20 minutes after crimping | bonding, and the tape 18 was affixed on the test plate 17. The tape 18 was removed from the end of the test plate 17 to a place where the width m was 25 mm, and the test plate 17 was attached to the lower handle of the tension tester. The tip of the peeled tape 18 was bent by 180 °, and the tape 18 was attached to the upper hand opening so that the tape 18 was straight off. At a tensile rate of 20 mm / min, the force to remove the tape 18 from the test plate 17 with a tester was measured. As a value, the average of the part from which the tape 18 was removed smoothly was made into the measured value. The results are shown in Table 11.

Comparative Examples 15-16

(Non-tackiness test of PFA film without functional group)

A non-tackiness test was carried out in the same manner as in Example 17 using an extruded film of PFA containing no functional group obtained in Production Example 14 (Comparative Example 15) and a glass plate coated with nothing (Comparative Example 16). The results are shown in Table 11.

From Table 11, it was found that PFA containing an OH group also had approximately the same excellent non-tackiness as PFA containing no functional group.

Example 19

(Adhesion heat resistance of hydroxyl group-containing PFA powder coating plate)

(1) Preparation of powder coating plate

PFA powder coating having a hydroxyl group obtained in Preparation Example 7 on an aluminum plate subjected to pretreatment in the same manner as in Example 7 was electrostatically charged at room voltage to 40 kPa using an electrostatic powder coating machine (the same as in Example 8). Painted. The coating plate was baked at 330 ° C. for 15 minutes to obtain a coating film. Further, on the obtained coating film, electrostatic coating was carried out in the same manner as above using PFA powder coating (manufactured by Daisen Kogyo Co., Ltd., neoprene PFA powder coating ACX-31) having no functional group, and at 20 ° C. at 380 ° C. It baked for min and obtained the transparent coating film of 159 micrometers in total.

(2) Measurement of adhesive strength

The schematic perspective view of the aluminum plate which has the coating film obtained in (1) of Example 19 in FIG. 16 is shown. As shown in Fig. 16, a sheath was placed in the coating film 20 obtained in the above (1) until the substrate was completely reached with a cutter at intervals of width n (10 mm). One end was bent to obtain a measuring instrument for measuring adhesive strength. The schematic perspective view of the measuring mechanism for measuring adhesive strength obtained in FIG. 17 is shown.

As shown in FIG. 17, the coating film 20 was pulled with respect to the aluminum plate 21 at 90 degreeC, and peeling strength was measured. The measurement was carried out using a Tenshirron universal testing machine (the same as in Example 7) at a crosshead speed of 50 mm / min at room temperature, the average peeling load by the area method was the value of the adhesive strength. The results are shown in Table 12.

(3) Measurement of adhesive heat resistance

The powder coating plate was separately prepared in the same manner as in (1) above, placed in a hot air dryer set at 300 ° C., the coating plate was taken out after 200 hours and after 500 hours, and cooled to room temperature. In the same manner as the above), the measurement instrument was manufactured and the adhesive strength was measured. The results are shown in Table 12.

Comparative Example 17

(Adhesion Heat Resistance of Powder Coating Plate Using Primer as Adhesive Layer)

(1) Coating of primer

A heat-resistant primer for fluororesin paint (polypropylene TFE enamel EK1959DGN manufactured by Daison Kogyo Co., Ltd.) was applied to an aluminum plate subjected to the same pretreatment as in Example 7 so as to have a film thickness of about 10 μm by spraying, It was baked for a minute.

(2) Preparation of powder coating plate

The electrostatic coating was carried out in the same manner as in Example 19 (1) using only the PFA powder coating (the same as in Example 19) containing no functional group on the primer coating plate of (1), and at 380 ° C. for 20 minutes. It calcined and it combined with the primer layer and obtained the coating film of 126 micrometers.

(3) Measurement of adhesive strength

Example 19 It carried out in the same manner as in (2). The results are shown in Table 12.

(4) Measurement of adhesive heat resistance

It carried out in the same manner as in Example 19 (3). The results are shown in Table 12.

Examples 20-21

(Adhesion heat resistance of hydroxyl group-containing PFA powder coating plate)

Instead of the aluminum plate, the powder coating plate was applied in the same manner as in Example 19, except that each of the SUS430 steel sheet (Example 20) pretreated with the aluminum plate and the galvanized steel sheet (Example 21) with only the degreasing treatment was used. Preparation and measurement of adhesive strength and adhesive heat resistance were carried out. The results are shown in Table 12.

Comparative Examples 18 to 19

(Adhesion Heat Resistance of Powder Coating Plate Using Primer as Adhesive Layer)

Instead of the aluminum plate, except that the SUS430 steel sheet (Comparative Example 18) pretreated in the same manner as the aluminum plate and each of the galvanized steel sheets (Comparative Example 19) subjected to only degreasing treatment were used, the production of the coated plate was carried out in the same manner as in Comparative Example 17. Adhesive strength and adhesive heat resistance were measured. The results are shown in Table 12.

Example 22

(Adhesion heat resistance of hydroxyl group-containing PFA laminate plate)

(1) Manufacture of Laminate Plates

An aluminum plate pretreated in the same manner as in Example 7 was used as the substrate. PFA film having a hydroxyl group obtained in Production Example 13 (thickness 100 μm) and PFA film containing no functional group (Neopron PFA film, manufactured by Daison Kogyo Co., Ltd., AF-0100) (thickness 100 μm) and peeling The polyimide film (the same thing as Example 15) of the dragon was cut | disconnected to the same size as the base material.

18 is a schematic cross-sectional view of the laminate test plate. As shown in FIG. 18, said hydroxyl group containing PFA film 23, the film 24 containing no functional group, and the polyimide film 25 were sandwiched between two aluminum plates (one is a base material; 22). It set in the press set to 350 degreeC, preheated (20 minutes), and heated at 50 kgf / cm <2> for 1 minute. After cooling, the aluminum plate 22 and the polyimide film 25 in contact with the polyimide film 25 were removed, and the aluminum plate 22 and the PFA film 24 having the hydroxyl group-containing PFA film 23 as an adhesive layer were used. ), A three-layer laminate was obtained. The schematic sectional drawing of the 3-layer laminated body obtained in FIG. 19 is shown.

(2) adhesive strength

Instead of the powder coating plate obtained in Example 19 (1), using the laminate plate (3-layer laminate) obtained in the above (1), sheaths were placed at intervals of 10 mm in the same manner as in Example 19 (2). One end of each rectangular film was bent at an interface between an aluminum plate and a PFA film layer containing a hydroxyl group to prepare a measuring instrument for measuring adhesive strength. The measurement of adhesive strength was carried out by pulling the film bent in the same manner as in Example 19 (2) at an angle of 90 ° with respect to the substrate. The results are shown in Table 13.

(3) Measurement of adhesive heat resistance

The laminated board of said (1) was manufactured separately, and it measured using the same method as Example 19 (3) using this. The results are shown in Table 13.

Examples 23-24

(Adhesion heat resistance of hydroxyl group-containing PFA laminate plate)

Instead of an aluminum plate, a laminate plate was produced in the same manner as in Example 22 except that each of the SUS430 steel sheet (Example 23) subjected to the same pretreatment as the aluminum plate and the galvanized steel sheet (Example 24) subjected to the degreasing treatment alone was used. Adhesive strength and adhesive heat resistance were measured. The results are shown in Table 13.

Comparative Example 20

(Adhesion Heat Resistance of Laminate Plate Using Surface-treated Fluorine Resin Film)

(1) Surface treatment of fluororesin film

One side of the PFA film (neopron PFA film AF-0100 manufactured by Daisen Kogyo Co., Ltd.) (thickness 100 μm) containing no functional group was transferred to tetra-etch A (JK Kosha) in the following manner. Surface treatment was performed. One side (adhesive side) of the PFA film was wiped with acetone, and after drying, the solution of tetra-etch A was applied to the surface, and the tetra-etch A solution was kept on the film for about 20 seconds to wash with methanol and pure water. And dried. The treated surface turned brown. Moreover, based on the wetness test method of the film of JISK-6768, when the wettability of the process surface was confirmed using the standard liquid of 40 dyn / cm, it was similarly wet and confirmed that it was fully processed. Moreover, the logarithmic adhesion angle of the process surface was 61 degree (the process surface is 110 degree).

(2) Preparation of Laminate Plate

A two-liquid mixed heat-resistant epoxy adhesive (High Temp HT-100L manufactured by Nikon Corporation) was applied to an aluminum plate subjected to the same pretreatment as in Example 7. The PFA film surface-treated in the above (1) was cut to the same size as the substrate, and the treated surface side was overlapped and adhered to the adhesive layer of the substrate, heated at 120 ° C for 1 hour, and then baked at 180 ° C for 20 hours, and cured and bonded. I was.

(3) Measurement of adhesive strength

Instead of the laminate plate obtained in Example 22, using the laminate plate obtained in the above (2), sheaths were inserted at intervals of 10 mm in the same manner as in Example 22 (2), and one end of each rectangular film was removed. A measuring instrument for measuring adhesive strength was prepared by bending at the interface between the PFA film and the adhesive layer. The adhesive strength was measured by pulling the bent film at an angle of 90 ° with respect to the substrate in the same manner as in Example 19 (2). The results are shown in Table 13.

(4) Measurement of adhesive heat resistance

The laminated plate of said (2) was manufactured separately, and it measured using the same method as Example 19 (3) using this. The results are shown in Table 13.

Comparative Examples 21 to 22

(Adhesion Heat Resistance of Laminate Plate Using Surface-treated Fluorine Resin Film)

Instead of the aluminum plate, the fluorine resin film was prepared in the same manner as in Comparative Example 20 except that each of the SUS430 steel sheet (Comparative Example 21) subjected to the same pretreatment as the aluminum plate and the galvanized steel sheet (Comparative Example 22) subjected to the degreasing treatment alone was used. The surface treatment, the manufacture of the laminate plate, the adhesive strength and the adhesive heat resistance were measured. The results are shown in Table 13.

Comparative Example 23

(Adhesion Heat Resistance of Laminate Plate Using Surface Treatment Film)

(1) Surface treatment of fluororesin film

Surface-treated FEP film (Neopron FEP film, NF-0100B1, single-sided processed product) manufactured by Daisen Kogyo Co., Ltd. instead of PFA film surface-treated with tetra-etch as described in Comparative Example 20 (1) (thickness 100 µm) Was used.

(2) Preparation of Laminate Plate

Instead of the PFA film surface-treated with tetra-etch, the same method as in Comparative Example 20 (2) was used except that the surface-treated FEP film of the above (1) was applied, and the epoxy adhesive was applied to the pretreated aluminum sheet, and the surface-treated film was laminated. Was carried out.

(3) Measurement of adhesive strength

Preparation of the measuring instrument and measurement of the adhesive strength were carried out in the same manner as in Comparative Example 20 except that the laminate plate obtained in (2) was used instead of the laminate plate using tetraetched PFA obtained in Comparative Example 20 (2). Was carried out.

(4) Measurement of adhesive heat resistance

The laminated board of said (2) was manufactured separately, and it measured in the same way as Example 19 (3) using this. The results are shown in Table 13.

Comparative Examples 24 to 25

(Adhesion Heat Resistance of Laminate Plate Using Surface-treated Fluorine Resin Film)

Instead of an aluminum plate, a laminate plate was produced in the same manner as in Comparative Example 23 except that each of the SUS430 steel sheet (Comparative Example 24) subjected to the same pretreatment as the aluminum plate and the galvanized steel sheet (Comparative Example 25) subjected to only degreasing treatment was used. And adhesive strength and adhesive heat resistance were measured. The results are shown in Table 13.

According to the present invention, a composite material for a cooking appliance obtained by applying a material made of a fluorine-containing polymer excellent in adhesion to a substrate to a substrate without requiring complicated steps. In addition, according to the present invention, a composite material for a cooking appliance excellent in heat resistance, non-adhesiveness, antifouling property, water and oil repellency, decontamination property, chemical resistance, rust resistance, antibacterial property, energy ray resistance and low friction resistance can be obtained.

Claims (41)

(a) 0.05 to 30 mol% of at least one monomer of the functional group-containing fluorinated ethylenic monomer having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, a carbonate group, a carboxyester group and an epoxy group, (b) a material comprising a functional group-containing fluorine-containing ethylenic polymer having a functional group formed by copolymerizing 70 to 99.95 mol% of one or more monomers of the fluorine-containing ethylenic monomer having no functional group as described above is applied. Composite for cooking appliances. The method according to claim 1, wherein the functional group-containing fluorine-containing ethylenic monomer (a) is represented by Formula (1): CX ₂ = CX ¹ -R _f -Y (1) (Wherein Y is —CH ₂ OH, —COOH, carbonate, carboxyester group or epoxy group, X and X ¹ are the same or differently hydrogen or fluorine atom, R _f is divalent fluorinated alkyl having 1 to 40 carbon atoms) 1 type represented by a len group, a C1-C40 fluorine-containing oxyalkylene group, a C1-C40 ether group containing a C1-C40 ether group, or a C1-C40 ether bond). A composite material for a cooking appliance, comprising the functional group-containing fluorine-containing ethylenic polymer which is the functional group-containing fluorine-containing ethylenic monomer described above applied to a substrate. The composite material for a cooking appliance according to claim 1, wherein the fluorine-containing ethylenic monomer (b) having no functional group is formed by applying a functional group-containing fluorine-containing ethylenic copolymer of tetrafluoroethylene to the substrate. The fluorine-containing ethylenic monomer (b) having no functional group is 85 to 99.7 mol% of tetrafluoroethylene and has the formula (2): CF ₂ = CF-R _f ¹ (2) (Wherein R _f ¹ is CF ₃ or OR _f ² (R _f ² is a C 1-5 perfluoroalkyl group) a functional group-containing fluorinated ethylenic polymer which is a mixed monomer with 0.3 to 15 mol% of monomers Composite material for a cooking appliance, characterized in that made by applying. The mixed monomer according to claim 1, wherein the fluorinated ethylenic monomer (b) having no functional group is a mixed monomer of 40 to 80 mol% of tetrafluoroethylene, 20 to 60 mol% of ethylene and other copolymerizable monomers of 0 to 15 mol%. A composite material for a cooking appliance, comprising a phosphorus functional group-containing fluorine-containing ethylenic polymer applied to a substrate. The composite material for a cooking appliance according to any one of claims 1 to 5, wherein the functional group-containing fluorine-containing ethylenic polymer is applied to the substrate in the form of a paint. The composite material for a cooking appliance according to any one of claims 1 to 4, wherein the functional group-containing fluorinated ethylenic polymer is applied to the substrate in the form of an aqueous acid solution. The composite material for a cooking appliance according to any one of claims 1 to 5, wherein the functional group-containing fluorine-containing ethylenic polymer is applied to the substrate in the form of powder coating. The composite material for a cooking appliance according to any one of claims 1 to 5, wherein the functional group-containing fluorine-containing ethylenic polymer is applied to the substrate in the form of a film. The composite material for a cooking appliance according to any one of claims 1 to 5, wherein the base material is a metal base material. The composite material for a cooking appliance according to any one of claims 1 to 5, wherein the base material is a glass substrate. A cooking appliance characterized by using the composite material for a cooking appliance according to claim 1. Heating cooker characterized in that using the composite for cooking appliances according to claim 1. Hot plate, characterized in that using the composite for cooking appliances according to claim 1. A hot plate comprising the composite for cooking appliance according to claim 3 or 4 for a metal heating surface. A hot plate comprising the lid for a glass of the cooking appliance composite according to claim 4 or 5. An oven range characterized by using a composite material for a cooking appliance according to claim 1. An oven range, characterized in that the composite for cooking appliance according to claim 3 or 4 is used on a metal inner surface. An oven range, characterized in that the cooking plate composite according to claim 3 or 4 is used for a cooking plate. An oven range, characterized in that the composite for cooking appliance according to claim 4 is used for a glass door. A heating pan, comprising the composite material for a cooking appliance according to claim 1. A cooking pot, characterized in that the composite for cooking appliance according to claim 3 or 4 is used for a metal heating surface. A cooking pot, comprising using the cooking appliance composite according to claim 4 or 5 in a lid made of glass. A frying pan, characterized by using the composite material for a cooking appliance according to claim 1. A frying pan characterized by using the cooking appliance composite according to claim 3 or 4 for a metal heating surface. A fryer comprising the composite material for a cooking appliance according to claim 1. A fryer comprising the composite for cooking appliance according to claim 3 or 4 on an inner surface of a metal. A fryer comprising the composite for cooking appliance according to claim 4 on the inner surface of glass. Rice cooker, characterized in that using the composite for cooking appliances according to claim 1 or 2. A cooker characterized in that the composite for cooking appliances according to claim 3 or 4 is used on an inner surface of a metal. A cooker characterized in that the composite for cooking appliance according to claim 3 or 4 is used for a metal inner lid. A complex characterized by using the composite for cooking appliance according to claim 1. A complex characterized in that the composite for cooking appliance according to claim 3 or 4 is used on a metal inner surface. A complex characterized in that the composite for cooking appliance according to claim 3 or 4 is used for a metal inner lid. Tableware or a container, characterized in that using the composite for cooking appliances according to claim 1 or 2. Metal tableware or a container made of a composite material for a cooking appliance according to any one of claims 3 to 5. Glass tableware or a container comprising the composite for cooking appliances according to claim 4. A cooking appliance for food processing, comprising using the cooking appliance composite according to claim 1. A cooking appliance for food mixing, characterized in that using the composite for cooking appliance according to claim 1. A cooking appliance for cutting food, characterized in that made using a composite material for cooking appliances according to claim 1. The bakery device characterized by using the composite material for cooking appliances according to claim 1.